CN116648765A

CN116648765A - Ionic polymers and copolymers

Info

Publication number: CN116648765A
Application number: CN202180085714.5A
Authority: CN
Inventors: L·王; Z·霍; C·沈
Original assignee: Shiyi Co
Current assignee: Shiyi Co
Priority date: 2020-10-20
Filing date: 2021-10-20
Publication date: 2023-08-25
Also published as: WO2022087169A1; AU2021364759A1; KR20230092977A; JP2023547823A; EP4232197A1; CA3196183A1; US20220119641A1; AU2021364759A9

Abstract

The present disclosure relates to compositions comprising a first polymer structure and a second polymer structure, wherein at least one of these may comprise an ionizable or ionic moiety. Materials, devices, and methods of using such compositions are also described.

Description

Ionic polymers and copolymers

Incorporation of reference

PCT request tables are filed concurrently with this specification as part of the present application. Each application of the claimed or priority of the application as indicated in the concurrently filed PCT application forms is hereby incorporated by reference in its entirety and for all purposes. The present application claims the benefit of U.S. provisional patent application No. 63/093,791 filed on 10/20/2020, which is incorporated herein by reference in its entirety.

Technical Field

Background

One component of an electrochemical cell includes a polymer-based electrolyte membrane. The physical and chemical properties of the polymer film can affect the performance of such a battery.

Disclosure of Invention

The present disclosure relates to compositions comprising a first polymer structure and a second polymer structure, wherein at least one of these comprises an ionizable or ionic moiety. The composition may include polymers, copolymers, polymer blends, block copolymers, or other polymer-based forms.

Thus, in a first aspect, the present disclosure encompasses a composition comprising a first structure, wherein:

(i) The first structure includes:

or a salt thereof, wherein:

R ⁷ and R is ⁸ Each of which is independently an electron withdrawing moiety, H, an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted heteroaliphatic group, an optionally substituted heteroalkyl group, an optionally substituted aromatic group, an optionally substituted aryl group, or an optionally substituted arylalkylene group, wherein R ⁷ Or R is ⁸ At least one of which comprises an electron withdrawing moiety or wherein R ⁷ And R is ⁸ May together form an optionally substituted cyclic group (e.g., which may be optionally substituted with an ionizable or ionic moiety);

R ⁹ and R is ¹⁰ Each of which is independently H, an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted heteroaliphatic group, an optionally substituted heteroalkyl group, an optionally substituted aromatic group, an optionally substituted aryl group, or an optionally substituted arylalkylene group, or wherein R ⁹ Or R is ¹⁰ Can together form an optionally substituted ringA labile group (e.g., which may be optionally substituted with an ionizable or ionic moiety);

ar comprises either an optionally substituted aromatic group or an optionally substituted arylene group;

n is an integer of 1 or more;

each of ring a, ring b, and/or ring c may be optionally substituted; and

wherein rings a-c, R ⁷ 、R ⁸ 、R ⁹ And R is ¹⁰ Optionally including an ionizable or ionic moiety.

In a second aspect, the present disclosure encompasses a composition comprising a first structure and a second structure, wherein:

(i) The first structure includes:

or a salt thereof, wherein:

R ⁹ and R is ¹⁰ Each of which is independently H, an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted heteroaliphatic group, an optionally substituted heteroalkyl group, an optionally substituted aromatic group, an optionally substituted aryl group, or an optionally substituted arylalkylene group, or wherein R ⁹ Or R is ¹⁰ May together form an optionally substituted cyclic group (e.g., which may be optionally substituted with an ionizable or ionic moiety);

n is an integer of 1 or more;

each of ring a, ring b, and/or ring c may be optionally substituted; and

wherein rings a-c, R ⁷ 、R ⁸ 、R ⁹ And R is ¹⁰ Optionally including an ionizable or ionic moiety; and

(i i) the second structure comprises an optionally substituted aromatic group or an optionally substituted arylene group.

In some embodiments (e.g., (i i)), the second structure comprises:

or a salt thereof, wherein:

R ¹ 、R ² 、R ³ 、R ⁷ 、R ⁸ 、R ⁹ and R is ¹⁰ Each of which is independently an electron withdrawing moiety, H, an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted heteroaliphatic group, an optionally substituted heteroalkyl group, an optionally substituted aromatic group, an optionally substituted aryl group, an optionally substituted aryloxy group, or an optionally substituted arylalkylene group, wherein R ⁷ And R is ⁸ May together form an optionally substituted cyclic group (e.g. which may be optionally substituted with an ionisable moiety or an ionic moiety) or wherein R ⁹ And R is ¹⁰ May together form an optionally substituted cyclic group (e.g., which may be optionally substituted with an ionizable or ionic moiety);

Each Ak comprises or is an optionally substituted alkylene;

L、L ¹ 、L ² 、L ³ and L ⁴ Independently a linking moiety;

each of m, m1, m2, m3, and m4 is independently an integer of 1 or more;

q is 0, 1, 2 or greater;

each of rings a-i may be optionally substituted; and

wherein rings a-i, R ⁷ 、R ⁸ 、R ⁹ And R is ¹⁰ Optionally including an ionizable or ionic moiety.

In any of the embodiments herein, the first structure comprises an ionizable or ionic moiety. In particular embodiments, R ⁷ Is an electron withdrawing moiety and R ⁸ Including an ionizable or ionic moiety.

In any embodiment herein, R ⁷ And R is ⁸ Can together form an optionally substituted cyclic group, or R ⁹ And R is ¹⁰ Together, optionally substituted cyclic groups may be formed. In certain embodiments, the optionally substituted cyclic group may be optionally substituted with an ionizable or ionic moiety.

In any embodiment herein, the second structure comprises an ionizable or ionic moiety. In other embodiments, both the first structure and the second structure independently comprise an ionizable moiety or an ionic moiety.

In any embodiment herein, at least one of rings a-i comprises an ionizable or ionic moiety.

In any embodiment herein, R ⁸ Including an ionizable or ionic moiety.

In any embodiment herein, the linking moiety is or includesCovalent bond, -O-, -SO ₂ -、-NR ^N1 -C (O) -, optionally substituted aliphatic, optionally substituted alkylene, optionally substituted haloalkylene, optionally substituted hydroxyalkylene, optionally substituted alkyleneoxy, optionally substituted heteroaliphatic, optionally substituted heteroalkylene, optionally substituted aromatic, optionally substituted arylene, optionally substituted aryleneoxy, optionally substituted heterocycle, or optionally substituted heterocyclediyl.

In any embodiment herein, the electron withdrawing moiety is an optionally substituted haloalkyl, cyano (CN), phosphate (e.g., -O (p=o) (OR) ^P1 )(OR ^P2 ) OR-O- [ P (=O) (OR) ^P1 )-O] _P3 -R ^P2 ) Sulfate ester group (e.g. -O-S (=O) ₂ (OR ^S1 ) Sulfonic acid group (-SO) ₃ H) Sulfonyl groups (e.g. -SO) ₂ -CF ₃ ) Difluoroborane (-BF) ₂ ) Dihydroxyboron (-B (OH)) ₂ ) Thiocyanato (-SCN) or piperidine

In any embodiment herein, the ionizable or ionic moiety comprises-L ^A -X ^A or-L ^A -(L ^A’ -X ^A ) _L2 or-L ^A -(X ^A -L ^A’ -X ^A’ ) _L2 or-L ^A -X ^A -L ^A’ -X ^A’ or-L ^A -X ^A -L ^A’ -X ^A’ -L ^A” -X ^A” Wherein each L ^A 、L ^A’ And L ^A” Is a connecting structure part; each X is ^A 、X ^A’ And X ^A” Independently comprising an acidic moiety, a basic moiety, or a polyionic moiety; and L2 is an integer of 1 or more. In some embodiments, each L ^A 、L ^A’ And L ^A” Independently include optionally substituted alkylene, optionally substituted alkyleneoxy, optionally substituted heteroalkylene, optionally substituted arylene, and/or optionally substituted aryleneoxy. In other embodiments, each X ^A 、X ^A’ And X ^A” Independently include sulfonic acid groups (-SO) ₂ OH), sulfonate anions (-SO) ₂ O ^- ) Sulfonium cations (e.g. -SR ^S1 R ^S2 ) Carboxyl (-CO) ₂ H) Carboxylate anions (-CO) ₂ ^- ) Phosphonic acid groups (e.g. -P (=o) (OH) ₂ ) Phosphonate anions (e.g. -P (=o) (O) ^- ) ₂ or-P (=O) (OH) (O ^- ))、Cations (e.g. -P) ⁺ R ^P1 R ^P2 R ^P3 ) Phosphazene->Cations (e.g. -P) ⁺ (＝NR ^N1 R ^N2 )R ^P1 R ^P2 ) Amino (e.g. -NR) ^N1 R ^N2 ) Ammonium cations (e.g. -N) ⁺ R ^N1 R ^N2 R ^N3 or-N ⁺ R ^N1 R ^N2 (-), heterocyclic cation, piperidine->Cation, azepane->Cations or their salt forms.

In any embodiment herein, the optionally substituted arylene or optionally substituted ring a-i is substituted with one or more substituents, and wherein the substituents are selected from the group consisting of: alkyl, alkoxy, alkoxyalkyl, amino, aminoalkyl, aryl, arylalkylene, aroyl, aryloxy, arylalkoxy, cyano, hydroxy, hydroxyalkyl, nitro, halo, and haloalkyl.

In any of the embodiments herein, the composition comprises a polymer or copolymer.

In any of the embodiments herein, the composition comprises a film (fi lm), membrane (membrane), or crosslinked polymer matrix.

In a third aspect, the disclosure features an electrochemical cell including: an anode; a cathode; and a polymer electrolyte membrane disposed between the anode and the cathode. In some embodiments, the polymer electrolyte membrane comprises any of the compositions described herein.

In a fourth aspect, the disclosure features a method of preparing a polymer, the method comprising: providing a first polymer unit and optionally a second polymer unit in the presence of a friedel-crafts alkylating agent, wherein the friedel-crafts alkylating agent comprises optionally a haloalkyl group and a reactive group, thereby forming an initial polymer having reactive groups; and replacing the reactive group with an ionic moiety, thereby providing an ionic polymer. In some embodiments, the ionic polymer comprises any of the compositions described herein.

In a fifth aspect, the disclosure features a method of making a copolymer, the method comprising: providing a first polymer unit and a second polymer unit in the presence of a friedel-crafts alkylating agent, wherein the friedel-crafts alkylating agent comprises optionally a haloalkyl group and a reactive group, thereby forming an initial copolymer having the reactive group; and replacing the reactive group with an ionic moiety, thereby providing an ionic copolymer. In some embodiments, the ionic copolymer comprises any of the compositions described herein.

In a sixth aspect, the disclosure features a method of making a copolymer, the method comprising: providing an initial copolymer having at least one aromatic or aryl group; reacting an aryl group with a haloalkylating agent or friedel-crafts alkylating agent, wherein friedel-crafts alkylating agent comprises a reactive group, thereby forming an initial copolymer having a halo group or reactive group; and replacing the halide or reactive group with an ionic moiety, thereby providing an ionic copolymer. In some embodiments, the ionic polymer comprises any of the compositions described herein. Additional details are as follows.

Definition of the definition

As used herein, the term "about" means +/-10% of any stated value. As used herein, this term modifies any recited value, range of values, or end point of one or more ranges.

As used herein, the terms "top," "bottom," "upper," "lower," "above," and "below" are used to provide a relative relationship between structures. The use of these terms does not denote or require that a particular structure be located at a particular position in the device.

"aliphatic radical" means a radical having from at least one carbon atom to 50 carbon atoms (C _1-50 ) For example one to 25 carbon atoms (C _1-25 ) Or one to ten carbon atoms (C _1-10 ) And it includes alkanes (or alkyl groups), alkenes (or alkenyl groups), alkynes (or alkynyl groups), including their cyclic forms, and also includes straight and branched chain arrangements, and all stereoisomers and positional isomers. Such aliphatic groups may be unsubstituted or substituted with one or more groups, such as those described herein with respect to alkyl groups.

The term "acyl" or "alkanoyl" is used interchangeably herein to denote an alkyl group as defined herein or hydrogen attached to a parent molecular group through a carbonyl group as defined herein. Such groups are exemplified by formyl, acetyl, propionyl, butyryl, and the like. Alkanoyl groups may be substituted or unsubstituted. For example, an alkanoyl group may be substituted with one or more substituents as described herein with respect to alkyl. In some embodiments, the unsubstituted acyl group is C _2-7 Acyl or alkanoyl groups. In a particular embodiment, the alkanoyl group is-C (O) -Ak, wherein Ak is an alkyl group as defined herein.

"alkoxy" refers to-OR, wherein R is an optionally substituted alkyl group as described herein. Exemplary alkoxy groups include methoxy, ethoxy, butoxy, trihaloalkoxy, such as trifluoromethoxy, and the like. The alkoxy group may be substituted or unsubstituted. For example, an alkoxy group may be substituted with one or more substituents as described herein with respect to alkyl. Exemplary unsubstituted alkoxy groups include C _1-3 、C _1-6 、C _1-12 、C _1-16 、C _1-18 、C _1-20 Or C _1-24 Alkoxy groups。

"alkoxyalkyl" refers to an alkyl group as defined herein substituted with an alkoxy group as defined herein. Exemplary unsubstituted alkoxyalkyl groups include 2 to 12 carbons (C _2-12 Alkoxyalkyl) and those having an alkyl group of 1 to 6 carbons and an alkoxy group of 1 to 6 carbons (i.e., C) _1-6 alkoxy-C _1-6 Alkyl).

"alkyl" and the prefix "alk" refer to branched or unbranched saturated hydrocarbon groups of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like. The alkyl group may be cyclic (e.g. C _3-24 Cycloalkyl) or acyclic. The alkyl group may be branched or unbranched. The alkyl group may also be substituted or unsubstituted. For example, an alkyl group may be substituted with one, two, three substituents, or in the case of two or more carbon alkyl groups, four substituents independently selected from: (1) C (C) _1-6 Alkoxy (e.g., -O-Ak wherein Ak is optionally substituted C _1-6 An alkyl group); (2) C (C) _1-6 Alkylsulfinyl (e.g., -S (O) -Ak wherein Ak is optionally substituted C _1-6 An alkyl group); (3) C (C) _1-6 Alkylsulfonyl groups (e.g. -SO) ₂ Ak, wherein Ak is optionally substituted C _1-6 An alkyl group); (4) Amino (e.g. -NR) ^N1 R ^N2 Wherein R is ^N1 And R is ^N2 Each of which is independently H or optionally substituted alkyl, or R ^N1 And R is ^N2 Forms a heterocyclic group together with the nitrogen atom to which each is attached); (5) aryl; (6) Arylalkoxy (e.g., -O-L-Ar, wherein L is a divalent form of optionally substituted alkyl and Ar is optionally substituted aryl); (7) Aroyl (e.g., -C (O) -Ar, wherein Ar is optionally substituted aryl); (8) Azido (e.g. -N) ₃ ) The method comprises the steps of carrying out a first treatment on the surface of the (9) cyano (e.g., -CN); (10) a formaldehyde group (e.g., -C (O) H); (11) C (C) _3-8 Cycloalkyl groups (e.g. monovalent saturated or unsaturated non-aromatic cyclic C _3-8 A hydrocarbon group); (12)Halo (e.g., F, cl, br or I); (13) Heterocyclyl (e.g., a 5-membered ring, a 6-membered ring, or a 7-membered ring, which contains one, two, three, or four non-carbon heteroatoms, such as nitrogen, oxygen, phosphorus, sulfur, or halogen, unless otherwise specified); (14) Heterocyclyloxy (e.g., -O-Het, wherein Het is heterocyclyl, as described herein); (15) Heterocyclylacyl (e.g., -C (O) -Het, wherein Het is heterocyclyl, as described herein); (16) hydroxy (e.g., -OH); (17) an N-protected amino group; (18) Nitro (e.g. -NO) ₂ ) The method comprises the steps of carrying out a first treatment on the surface of the (19) Oxo (e.g., =o) or oxime (e.g., =n-OH); (20) C (C) _3-8 A spirocyclic group (e.g., an alkylene or heteroalkylenediyl group, both ends of which are bonded to the same carbon atom of the parent group); (21) C (C) _1-6 Thioalkoxy (e.g. -S-Ak, wherein Ak is optionally substituted C _1-6 An alkyl group); (22) a thiol group (e.g., -SH); (23) -CO ₂ R ^A Wherein R is ^A Selected from (a) hydrogen, (b) C _1-6 Alkyl, (C) C _4-18 Aryl and (d) (C _4-18 Aryl) C _1-6 Alkyl (e.g., -L-Ar, wherein L is a divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl); (24) -C (O) NR ^B R ^C Wherein R is ^B And R is ^C Each of (a) hydrogen, (b) C _1-6 Alkyl, (C) C _4-18 Aryl and (d) (C _4-18 Aryl) C _1-6 Alkyl (e.g., -L-Ar, wherein L is a divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl); (25) -SO ₂ R ^D Wherein R is ^D Selected from (a) C _1-6 Alkyl, (b) C _4-18 Aryl and (C) (C _4-18 Aryl) C _1-6 Alkyl (e.g., -L-Ar, wherein L is a divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl); (26) -SO ₂ NR ^E R ^F Wherein R is ^E And R is ^F Each of (a) hydrogen, (b) C _1-6 Alkyl, (C) C _4-18 Aryl and (d) (C _4-18 Aryl) C _1-6 Alkyl (e.g., -L-Ar, wherein L is a divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl); and (27) -NR ^G R ^H Wherein R is ^G And R is ^H Each of (a) is independently selected from hydrogen(b) an N-protecting group, (C) C _1-6 Alkyl, (d) C _2-6 Alkenyl (e.g. optionally substituted alkyl having one or more double bonds), (e) C _2-6 Alkynyl (e.g., optionally substituted alkyl having one or more triple bonds), (f) C _4-18 Aryl, (g) (C _4-18 Aryl) C _1-6 Alkyl (e.g., L-Ar, wherein L is a divalent form of optionally substituted alkyl group and Ar is optionally substituted aryl), (h) C _3-8 Cycloalkyl and (i) (C _3-8 Cycloalkyl) C _1-6 Alkyl (e.g., -L-Cy, wherein L is a divalent form of an optionally substituted alkyl group and Cy is an optionally substituted cycloalkyl group, as described herein), wherein in one embodiment no two groups are attached to the nitrogen atom through a carbonyl group or sulfonyl group. The alkyl group may be a primary, secondary or tertiary alkyl group substituted with one or more substituents (e.g., one or more halo or alkoxy groups). In some embodiments, the unsubstituted alkyl group is C _1-3 、C _1-6 、C _1-12 、C _1-16 、C _1-18 、C _1-20 Or C _1-24 An alkyl group.

"alkylene" refers to a multivalent (e.g., divalent, trivalent, tetravalent, etc.) form of an alkyl group, as described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, and the like. In some embodiments, the alkylene group is C _1-3 、C _1-6 、C _1-12 、C _1-16 、C _1-18 、C _1-20 、C _1-24 、C _2-3 、C _2-6 、C _2-12 、C _2-16 、C _2-18 、C _2-20 Or C _2-24 An alkylene group. The alkylene groups may be branched or unbranched. The alkylene group may be saturated or unsaturated (e.g., have one or more double or triple bonds). The alkylene groups may also be substituted or unsubstituted. For example, an alkylene group may be substituted with one or more substituents as described herein with respect to alkyl. In one instance, the substituted alkylene group can include an optionally substituted haloalkylene (e.g., an optionally substituted alkylene substituted with one or more hydroxyl groups as defined herein), an optionally substitutedA haloalkylene (e.g., an optionally substituted alkylene substituted with one or more halo groups as defined herein), and the like.

"Alkylene group" refers to an alkylene group as defined herein attached to a parent molecular group through an oxygen atom.

"amino" means-NR ^N1 R ^N2 Wherein R is ^N1 And R is ^N2 Independently is H, optionally substituted alkyl, optionally substituted cycloalkyl or optionally substituted aryl; or R is ^N1 And R is ^N2 Forms together with the nitrogen atom to which each is attached an optionally substituted heterocyclic group or heterocycle, as defined herein; or R is ^N1 And R is ^N2 Together forming an optionally substituted alkylene or heteroalkylene (e.g., as described herein).

"aminoalkyl" refers to an alkyl group, as defined herein, substituted with an amino group, as defined herein. Non-limiting aminoalkyl groups include-L-NR ^N1 R ^N2 Wherein L is a polyvalent alkyl group, as defined herein; r is R ^N1 And R is ^N2 Independently H, optionally substituted alkyl, or optionally substituted aryl; or R is ^N1 And R is ^N2 Together with the nitrogen atom to which each is attached, form a heterocyclic group, as defined herein.

"ammonium" is meant to include the protonated nitrogen atom N ⁺ Is a group of (2). Exemplary ammonium groups include-N ⁺ R ^N1 R ^N2 R ^N3 Wherein R is ^N1 、R ^N2 And R is ^N3 Independently is H, optionally substituted alkyl, optionally substituted cycloalkyl or optionally substituted aryl; or R is ^N1 And R is ^N2 Together with the nitrogen atom to which each is attached, form an optionally substituted heterocyclic group or heterocycle; or R is ^N1 And R is ^N2 Together forming an optionally substituted alkylene or heteroalkylene (e.g., as described herein); or R is ^N1 And R is ^N2 And R is ^N3 Together with the nitrogen atom to which each is attached, form an optionally substituted heterocyclic group or a heterocycle, for example a heterocyclic cation.

Unless otherwise specified, "aromatic group" refers to a cyclic, conjugated group or moiety of 5-15 ring atoms having a single ring (e.g., phenyl) or multiple condensed rings (wherein at least one ring is aromatic) (e.g., naphthyl, indolyl, or pyrazolopyridinyl); i.e., at least one ring and optionally a plurality of fused rings have a continuous delocalized pi-electron system. Typically, the out-of-plane pi-electron number corresponds to Hooke's law (4n+2). The point of attachment to the parent structure is typically through the aromatic portion of the fused ring system. Such aromatic groups may be unsubstituted or substituted with one or more groups, such as those described herein with respect to alkyl or aryl groups. Other substituents may include aliphatic groups, halogenated aliphatic groups, halo, nitrate, cyano, sulfonate, sulfonyl, or others.

"aryl" refers to a group containing any carbon-based aromatic group including, but not limited to, phenyl, benzyl, anthracenyl (anthracenyl), benzocyclobutenyl, benzocyclooctenyl, biphenyl,radicals (chrysenyl), indanyl, fluoranthenyl, indacenyl (indacenyl), indenyl, naphthyl, phenanthryl, phenoxybenzyl, picenyl (picenyl), pyrenyl, terphenyl, and the like, including fused benzo-C _4-8 Cycloalkyl groups (e.g., as defined herein), such as indanyl, tetrahydronaphthyl, fluorenyl, and the like. The term aryl also includes "heteroaryl" which is defined as an aromatic group-containing group having at least one heteroatom incorporated into the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term non-heteroaryl (which is also included in the term aryl) is defined as a group containing an aryl group that does not contain a heteroatom. The aryl group may be substituted or unsubstituted. The aryl group may be substituted with one, two, three, four or five substituents independently selected from: (1) C (C) _1-6 Alkanoyl (e.g., -C (O) -Ak wherein Ak is optionally substituted C _1-6 An alkyl group); (2) C (C) _1-6 An alkyl group; (3) C (C) _1-6 Alkoxy (e.g., -O-Ak wherein Ak is optionally substituted C _1-6 An alkyl group); (4) C (C) _1-6 alkoxy-C _1-6 Alkyl (e.g., -L-O-Ak wherein L is optionallyDivalent form of substituted alkyl and Ak is optionally substituted C _1-6 An alkyl group); (5) C (C) _1-6 Alkylsulfinyl (e.g., -S (O) -Ak wherein Ak is optionally substituted C _1-6 An alkyl group); (6) C (C) _1-6 alkylsulfinyl-C _1-6 Alkyl (e.g., -L-S (O) -Ak, wherein L is a divalent form of optionally substituted alkyl and Ak is optionally substituted C _1-6 An alkyl group); (7) C (C) _1-6 Alkylsulfonyl groups (e.g. -SO) ₂ Ak, wherein Ak is optionally substituted C _1-6 An alkyl group); (8) C (C) _1-6 alkylsulfonyl-C _1-6 Alkyl (e.g. -L-SO ₂ Ak, wherein L is a divalent form of optionally substituted alkyl and Ak is optionally substituted C _1-6 An alkyl group); (9) aryl; (10) Amino (e.g. -NR) ^N1 R ^N2 Wherein R is ^N1 And R is ^N2 Each of which is independently H or optionally substituted alkyl, or R ^N1 And R is ^N2 Forms a heterocyclic group together with the nitrogen atom to which each is attached); (11) C (C) _1-6 Aminoalkyl (e.g., by one or more-NR as described herein ^N1 R ^N2 An alkyl group as defined herein substituted with a group); (12) Heteroaryl (e.g., a subset of heterocyclyl (e.g., 5-membered ring, 6-membered ring, or 7-membered ring, which contains one, two, three, or four non-carbon heteroatoms, unless otherwise specified), which is aromatic); (13) (C) _4-18 Aryl) C _1-6 Alkyl (e.g., -L-Ar, wherein L is a divalent form of optionally substituted alkyl and Ar is optionally substituted aryl); (14) Aroyl (e.g., -C (O) -Ar, wherein Ar is optionally substituted aryl); (15) Azido (e.g. -N) ₃ ) The method comprises the steps of carrying out a first treatment on the surface of the (16) cyano (e.g., -CN); (17) C (C) _1-6 Azidoalkyl (e.g., an alkyl group as defined herein substituted with one or more azido groups as described herein); (18) a formaldehyde group (e.g., -C (O) H); (19) formaldehyde-C _1-6 Alkyl (e.g., an alkyl group as defined herein substituted with one or more formaldehyde groups as described herein); (20) C (C) _3-8 Cycloalkyl groups (e.g. monovalent saturated or unsaturated non-aromatic cyclic C _3-8 A hydrocarbon group); (21) (C) _3-8 Cycloalkyl) C _1-6 Alkyl (e.g., as defined herein substituted with one or more cycloalkyl groups as described herein)An alkyl group); (22) halo (e.g., F, cl, br or I); (23) C (C) _1-6 Haloalkyl (e.g., alkyl groups as defined herein substituted with one or more halo groups as described herein); (24) Heterocyclyl (e.g., a 5-membered ring, a 6-membered ring, or a 7-membered ring, which contains one, two, three, or four non-carbon heteroatoms, such as nitrogen, oxygen, phosphorus, sulfur, or halogen, unless otherwise specified); (25) Heterocyclyloxy (e.g., -O-Het, wherein Het is heterocyclyl as described herein); (26) Heterocyclylacyl (e.g., -C (O) -Het, wherein Het is heterocyclyl as described herein); (27) hydroxy (e.g. -OH); (28) C (C) _1-6 Hydroxyalkyl (e.g., an alkyl group as defined herein substituted with one or more hydroxy groups as described herein); (29) Nitro (e.g. -NO) ₂ )；(30)C _1-6 Nitroalkyl (e.g., an alkyl group as defined herein substituted with one or more nitro groups as described herein); (31) an N-protected amino group; (32) N-protected amino-C _1-6 Alkyl (e.g., an alkyl group as defined herein substituted with one or more N-protected amino groups); (33) Oxo (e.g., =o) or oxime (e.g., =n-OH); (34) C (C) _1-6 Thioalkoxy (e.g. -S-Ak, wherein Ak is optionally substituted C _1-6 An alkyl group); (35) thio-C _1-6 alkoxy-C _1-6 Alkyl (e.g., -L-S-Ak, wherein L is a divalent form of optionally substituted alkyl and Ak is optionally substituted C _1-6 An alkyl group); (36) - (CH) ₂ ) _r CO ₂ R ^A Wherein R is an integer from 0 to 4, and R ^A Selected from (a) hydrogen, (b) C _1-6 Alkyl, (C) C _4-18 Aryl and (d) (C _4-18 Aryl) C _1-6 Alkyl (e.g., -L-Ar, wherein L is a divalent form of optionally substituted alkyl and Ar is optionally substituted aryl); (37) - (CH) ₂ ) _r CONR ^B R ^C Wherein R is an integer from 0 to 4 and wherein each R ^B And R is ^C Independently selected from (a) hydrogen, (b) C _1-6 Alkyl, (C) C _4-18 Aryl (d) (C) _4-18 Aryl) C _1-6 Alkyl (e.g., -L-Ar, wherein L is a divalent form of optionally substituted alkyl and Ar is optionally substituted aryl); (38) - (CH) ₂ ) _r SO ₂ R ^D WhereinR is an integer from 0 to 4 and wherein R ^D Selected from (a) C _1-6 Alkyl, (b) C _4-18 Aryl and (C) (C _4-18 Aryl) C _1-6 Alkyl (e.g., -L-Ar, wherein L is a divalent form of optionally substituted alkyl and Ar is optionally substituted aryl); (39) - (CH) ₂ ) _r SO ₂ NR ^E R ^F Wherein R is an integer from 0 to 4 and wherein R ^E And R is ^F Each of (a) hydrogen, (b) C _1-6 Alkyl, (C) C _4-18 Aryl and (d) (C _4-18 Aryl) C _1-6 Alkyl (e.g., -L-Ar, wherein L is a divalent form of optionally substituted alkyl and Ar is optionally substituted aryl); (40) - (CH) ₂ ) _r NR ^G R ^H Wherein R is an integer from 0 to 4 and wherein R ^G And R is ^H Each of (a) hydrogen, (b) an N-protecting group, (C) C _1-6 Alkyl, (d) C _2-6 Alkenyl (e.g. optionally substituted alkyl having one or more double bonds), (e) C _2-6 Alkynyl (e.g., optionally substituted alkyl having one or more triple bonds), (f) C _4-18 Aryl, (g) (C _4-18 Aryl) C _1-6 Alkyl (e.g., -L-Ar, wherein L is a divalent form of optionally substituted alkyl and Ar is optionally substituted aryl), (h) C _3-8 Cycloalkyl and (i) (C _3-8 Cycloalkyl) C _1-6 Alkyl (e.g., -L-Cy, wherein L is a divalent form of optionally substituted alkyl and Cy is an optionally substituted cycloalkyl, as described herein), wherein in one embodiment no two groups are attached to the nitrogen atom through a carbonyl group or sulfonyl group; (41) thiol groups (e.g., -SH); (42) Perfluoroalkyl groups (e.g., alkyl groups in which each hydrogen atom is replaced with a fluorine atom); (43) Perfluoroalkoxy (e.g. -OR) ^f Wherein R is ^f An alkyl group in which each hydrogen atom is substituted with a fluorine atom); (44) Aryloxy (e.g., -OAr, wherein Ar is optionally substituted aryl); (45) A cycloalkoxy group (e.g., -O-Cy, wherein Cy is optionally substituted cycloalkyl, as described herein); (46) Cycloalkylalkoxy (e.g., -O-L-Cy, wherein L is a divalent form of optionally substituted alkyl and Cy is optionally substituted cycloalkyl, as described herein) and (47) arylalkoxy (e.g., -O-L-Ar, wherein L is optionally takenDivalent forms of substituted alkyl groups and Ar is optionally substituted aryl). In particular embodiments, the unsubstituted aryl group is C _4-18 、C _4-14 、C _4-12 、C _4-10 、C _6-18 、C _6-14 、C _6-12 Or C _6-10 An aryl group.

"arylalkyloxy" refers to an arylalkylene group attached to a parent molecular moiety through an oxygen atom, as defined herein. In some embodiments, the arylalkoxy group is-O-Ak-Ar, wherein Ak is optionally substituted alkylene, as defined herein, and Ar is optionally substituted aryl, as defined herein.

"(aryl) (alkyl) ene" refers to a divalent form comprising an arylene group as described herein attached to an alkylene or heteroalkylene group as described herein. In some embodiments, the (aryl) (alkyl) subunit group is-L-Ar-or-L-Ar-L-or-Ar-L-, wherein Ar is an arylene group and each L is independently an optionally substituted alkylene group or an optionally substituted heteroalkylene group.

"arylalkylene" refers to an aryl group as defined herein attached to a parent molecular moiety through an alkylene group as defined herein. In some embodiments, the arylalkylene groups are-Ak-Ar, wherein Ak is optionally substituted alkylene, as defined herein, and Ar is optionally substituted aryl, as defined herein. The arylalkylene groups may be substituted or unsubstituted. For example, an arylalkylene group can be substituted with one or more substituents as described herein for aryl and/or alkyl. Exemplary unsubstituted arylalkylene groups have 7 to 16 carbons (C _7-16 Arylalkylene) and those having an aryl group of 4 to 18 carbons and an alkylene group of 1 to 6 carbons (i.e. (C) _4-18 Aryl) C _1-6 An alkylene group).

"arylene" refers to a multivalent (e.g., divalent, trivalent, tetravalent, etc.) form of an aryl group as described herein. Exemplary arylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenyl ether, acenaphthylene, anthrylene, or phenanthrylene. In some embodiments, arylene groupsThe radical being C _4-18 、C _4-14 、C _4-12 、C _4-10 、C _6-18 、C _6-14 、C _6-12 Or C _6-10 Arylene groups. The arylene group may be branched or unbranched. Arylene groups may also be substituted or unsubstituted. For example, an arylene group may be substituted with one or more substituents as described herein with respect to aryl.

"arylene" refers to an arylene group as defined herein attached to a parent molecular group through an oxygen atom.

"aryloxy" refers to an aryl group as defined herein attached to the parent molecular moiety through an oxygen atom.

"aroyl" refers to an aryl group attached to the parent molecular group through a carbonyl group. In some embodiments, the unsubstituted aroyl group is C _7-11 Aroyl or C _5-19 Aroyl groups. In certain embodiments, the aroyl group is-C (O) -Ar, wherein Ar is an aryl group, as defined herein.

"borane" means-BR ₂ A group wherein each R may independently be H, halo, or optionally substituted alkyl.

"dihydroxyboron" means-BOH ₂ A group.

"carboxy" means-CO ₂ H groups.

"carboxylate anion" refers to-CO ₂ ^- A group.

"covalent bond" refers to a covalent bonding interaction between two components. Non-limiting covalent bonds include single bonds, double bonds, triple bonds, or spiro bonds, wherein at least two molecular groups are bound to the same carbon atom.

"cyano" refers to a-CN group.

"cyclic group" is used herein to refer to an aryl group, a non-aryl group (e.g., cycloalkyl or heterocycloalkyl group), or both. The cyclic group has one or more ring systems, which may be substituted or unsubstituted. The cyclic group may contain one or more aryl groups, one or more non-aryl groups, or one or more aryl groups and one or more non-aryl groups.

"cycloalkyl" refers to a monovalent saturated or unsaturated, non-aromatic cyclic hydrocarbon group of 3 to 10 carbons (e.g., C _3-8 Or C _3-10 ) Examples are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo [2.2.1 unless otherwise indicated.]Heptyl, and the like. The term cycloalkyl also includes "cycloalkenyl" defined as a non-aromatic carbon-based ring consisting of three to ten carbon atoms and containing at least one double bond, i.e. c=c. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, and the like. Cycloalkyl groups may also be substituted or unsubstituted. For example, cycloalkyl groups may be substituted with one or more groups including those described herein with respect to alkyl groups.

"halo" refers to F, cl, br or I.

"haloalkyl" refers to an alkyl group as defined herein substituted with one or more halo groups.

"haloalkylene" refers to an alkylene group as defined herein substituted with one or more halo groups.

"heteroaliphatic" refers to an aliphatic group as defined herein which includes at least 1 heteroatom to 20 heteroatoms, such as 1 to 15 heteroatoms, or 1 to 5 heteroatoms, which can be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof in the group.

"heteroalkyl" refers to an alkyl group as defined herein containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from nitrogen, oxygen, phosphorus, sulfur, selenium, or halogen).

"heteroalkylene" refers to an alkylene group as defined herein containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from nitrogen, oxygen, phosphorus, sulfur, selenium, or halogen). The heteroalkylene group can be saturated or unsaturated (e.g., having one or more double or triple bonds). The heteroalkylene group can be substituted or unsubstituted. For example, the heteroalkylene group can be substituted with one or more substituents as described herein with respect to the alkyl group.

"heteroaryl" refers to a subset of heterocyclyl groups as defined herein which are aromatic, i.e., they contain 4n+2 pi electrons within a single or multiple ring system.

The term "heterocycloalkyl" is a class of cycloalkyl groups as defined above wherein at least one of the carbon atoms and the hydrogen atoms to which they are attached (if present) is replaced by O, S, N or NH. The heterocycloalkyl group and heterocycloalkenyl group can be substituted or unsubstituted. Cycloalkenyl and heterocycloalkenyl groups can be substituted with one or more groups including, but not limited to, alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, sulfonic, sulfinic, fluoroacid, phosphonic, ester, ether, halo, hydroxy, keto, nitro, cyano, azido, silyl, sulfonyl, sulfinyl, or thiol groups, as described herein.

"heterocycle" refers to a compound having one or more heterocyclyl moieties. Non-limiting heterocycles include optionally substituted imidazoles, optionally substituted triazoles, optionally substituted tetrazoles, optionally substituted pyrazoles, optionally substituted imidazolines, optionally substituted pyrazolines, optionally substituted imidazolidines, optionally substituted pyrazolidines, optionally substituted pyrroles, optionally substituted pyrrolines, optionally substituted pyrrolidines, optionally substituted tetrahydrofurans, optionally substituted furans, optionally substituted thiophenes, optionally substituted pyrrolidines, optionally substituted thiophenesAzole, optionally substituted Iso->Oxazole, optionally substituted isothiazole, optionally substituted thiazole, optionally substituted oxathiolane, optionally substituted +.>Diazole, optionally substituted thiadiazole, optionally substituted sulfolane, optionally substituted succinimide, optionally substituted thiazolidinedione, optionally substituted +.>Oxazolidinone, optionally substituted hydantoin, optionally substituted pyridine, optionally substituted piperidine, optionally substituted pyridazine, optionally substituted piperazine, optionally substituted pyrimidine, optionally substituted pyrazine, optionally substituted triazine, optionally substituted pyran- >Optionally substituted tetrahydropyran, optionally substituted di->English, optionally substituted Di->An alkane, an optionally substituted dithiane, an optionally substituted trithiane, an optionally substituted thiopyran, an optionally substituted tetrahydrothiopyran, an optionally substituted +.>Oxazines, optionally substituted morpholines, optionally substituted thiazines, optionally substituted thiomorpholines, optionally substituted cytosines, optionally substituted thymines, optionally substituted uracils, optionally substituted thiomorpholines dioxide, optionally substituted indenes, optionally substituted indolines, optionally substituted indoles, optionally substituted isoindoles, optionally substituted indolizines, optionally substituted indazoles, optionally substituted benzimidazoles, optionally substituted azaindoles, optionally substituted azaindazoles, optionally substituted pyrazolopyrimidines, optionally substituted purines, optionally substituted benzofurans, optionally substituted isobenzofurans, optionally substituted benzothiophenes, optionally substituted benzisoids>Oxazole, optionally substituted anthranilic anhydride (anthranil), optionally substituted benzisothiazole, optionally substituted benzo +.>Oxazole, optionally substituted benzothiazole, optionally substituted benzothiadiazole, optionally substituted adenine, optionally substituted guanine, optionally substituted tetrahydroquinoline, optionally substituted dihydroquinoline, optionally substituted dihydroisoquinoline, optionally substituted quinoline, optionally substituted isoquinoline, optionally substituted quinolizine, optionally substituted quinoxaline, optionally substituted phthalazine, optionally substituted quinazoline, optionally substituted cinnoline, optionally substituted naphthyridine, optionally substituted pyridopyrimidine, optionally substituted pyridopyrazine, optionally substituted pteridine, optionally substituted chromene, optionally substituted isochromene, optionally substituted chromene, optionally substituted benzo- >Oxazines, optionally substituted quinolinones, optionally substituted isoquinolones, optionally substituted carbazoles, optionally substituted dibenzofurans, optionally substituted acridines, optionally substituted phenazines, optionally substituted phenones>Oxazine, optionally substituted phenothiazine, optionally substituted pheno ∈ ->Thia-, optionally substituted quinuclidine-, optionally substituted azaadamantane-, optionally substituted dihydroaza +.>Optionally substituted aza->(azepine), optionally substituted diaza->(diazepine), optionally substituted epoxyhexane, optionally substituted thietane (thiepine), optionally substituted thiazepine->(thiazepine), optionally substituted azacyclooctane (azocan), optionally substituted azine Xin Yin, optionally substituted thiacine (thiocane), optionally substituted azacyclononane (azocan), optionally substituted azine, and the like. Optional substituents include any of those described herein with respect to aryl. The heterocyclic ring may also include cations and/or salts of any of these (e.g., any of those described herein, e.g., optionally substituted piperidine->Optionally substituted pyrrolidino>Optionally substituted pyrazoles->Optionally substituted imidazoles>Optionally substituted pyridines>Optionally substituted quinolines->Optionally substituted isoquinolines- >Optionally substituted acridine>Optionally substituted phenanthridinium->Optionally substituted pyridazine->Optionally substitutedPyrimidine->Optionally substituted pyrazinyl->Optionally substituted phenazine->Or optionally substituted morpholino->)。

"heterocyclyl" means a 3-, 4-, 5-, 6-, or 7-membered ring (e.g., a 5-, 6-, or 7-membered ring) containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from nitrogen, oxygen, phosphorus, sulfur, selenium, or halogen) unless otherwise specified. The 3-membered ring has 0 to 1 double bond, the 4-membered ring and the 5-membered ring have 0 to 2 double bonds, and the 6-membered ring and the 7-membered ring have 0 to 3 double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic, and tetracyclic groups, wherein any of the above heterocyclic rings is fused to one, two, or three rings, which are independently selected from the group consisting of: aryl rings, cyclohexane rings, cyclohexene rings, cyclopentane rings, cyclopentene rings, and further monocyclic heterocyclic rings, such as indolyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, benzofuranyl, benzothienyl, and the like. Heterocycles include acridinyl, adenine, alloxazinyl, azaadamantyl, azabenzimidazolyl, azabicyclononyl, azepanyl, azacyclooctyl, azacyclononyl, azahypoxanthine, azaindazolyl, azaindolyl, azepinyl (azecinyl), azepanyl (azepanyl), aza An aryl (azepinyl), azetidinyl (azetidinyl), aziridinyl (aziridinyl), azetidinyl (azovinyl), azepanyl (azovinyl), benzimidazolyl, benzisothiazolyl,Benzohetero->Azolyl, benzodiazepine +.>Radical, benzodiazinocinyl, benzodihydrofuryl, benzodioxenyl, benzodi->English, benzodi->Alkyl, benzodioxaoctenyl (benzodioxanyl), benzodioxadienyl (benzodioxanyl), benzodithiocycloalkenyl (benzodithiepinyl), benzodithiinyl, benzodioxaoctenyl, benzofuranyl, benzophenazinyl, benzopyronyl, benzoquinolinyl, benzoquinolizinyl, benzothiadiazayl, and the like>Radical, benzothiadiazolyl, benzothiazepine->A radical, benzothiazecinyl (benzothiocinyl), benzothiazolyl, benzothienyl, benzothiazinonyl, benzothiazinyl, benzothiopyranyl, benzothiopyranonyl, benzotriazal >A radical, benzotriazinonyl, benzotriazinyl, benzotriazolyl, benzooxathidienyl, benzotrioxenyl, benzooxadiazepine->Radical, benzo oxygen sulfurAza->Radical, benzoxathionine radical, benzoxathiacin radical (benzothiocinyl), benzoxazepine radical>Radical, benzo->Oxazinyl, benzoxazepinyl, benzo->Azolinonyl (benzoxazol inonyl), benzo +.>Oxazolinyl (benzoxazolyl), benzo +.>Azolyl, benzylsultamyl (benzylsultamyl), benzylsultamyl (benzazeylsulfamoyl), bipyrazinyl, bipyridyl, carbazolyl (e.g. 4H-carbazolyl), carbolinyl (e.g. beta-carbolinyl), chromanyl, chromen-yl, cinnolinyl (cinnolinyl), coumarin, cytidinyl (cyldinyl), cytosine (cytosinyl), decahydroisoquinolyl, decahydroquinolinyl, diazabicyclooctyl, diazacyclobutenyl, diazapropylsulfinyl (diazidinyl), diazidinyl, diazirizinyl, dibenzoisoquinolinyl, dibenzoacridinyl, dibenzocarbazolyl, dibenzophenazinyl, dibenzopyronyl, dibenzophenonyl, dibenzoxanyl, dibenzoquinoxalinyl, dibenzothioquinoxalinyl, dibenzothiazyl >Radical, dibenzothiazetidinyl, dibenzothiazyl, dibenzooxazepinyl, dihydroaza ∈ ->A radical, a dihydroazebutyl radical, a dihydrofuryl radical, a dihydroisoquinolinyl radical, a dihydropyranyl radical dihydropyridinyl, dihydropyridinyl (dihydroypyridy), dihydroquinolinyl, dihydrothienyl, indolinyl, di->Alkyl, di->Oxazinyl, dihydroxyindolyl, ethylenedioxy, di-o>An english group, a dioxobenzofuranyl group, a dioxolyl group, a dioxotetrahydrofuranyl group, a dioxothiomorpholinyl group, a dithianyl group, a dithienyl group, a dithiinyl group, a furyl group, a furazanyl group (furazanyl group), a furoyl group (furoyl group), a furyl group (furyl group), a guanine group, a homopiperazinyl group, a homopiperidinyl group, a hypoxanthine group, a hydantoin group, an imidazolinidinyl group (imidozolidinyl group), an imidazolinyl group, a furoyl group (furoyl group), a guanyl group, a homopiperazinyl group, a homopiperidinyl group, a hypoxanthine group, a hydantoin group, an imidazolinyl group, a thiazolidinyl group, a imidazolyl, indazolyl (e.g., 1H-indazolyl), indolenyl (indolenyl), indolinyl, indolizinyl, indolyl (e.g., 1H-indolyl or 3H-indolyl), isatinyl (isatinyl), isatinyl (isattyl), isobenzofuranyl, isochromanyl, isoindolyl, isoindazolyl (isoindolyl, isopropyrazonyl), isopyrazolyl, isoisooxazolyl, and isopyrazoloyl >Oxazolidinyl, iso->Oxazolyl, isoquinolyl, isothiazolidinyl, isothiazolyl, morpholinyl, naphthoindazolyl, naphthoindolyl, naphthothiadinyl (naphthyridinyl), naphthopyranyl, naphthothiazolyl, naphthothionaphthyridinylOxathiolyl (napthothiolyl), naphthatriazolyl, naphthyridinyl (naphthyridinyl), octahydroisoquinolinyl, oxabicycloheptyl, oxauracil, and the like>Diazolyl,/->Oxazinyl, oxaaziridinyl, </i >>An oxazolidinyl group,Oxazolidone,/->Oxazolinyl group,/->Oxazolonyl,>oxazolyl, oxetanyl (oxyheptyl), oxetanonyl, oxetanyl (oxyyl), oxetanyl (oxetanyl), oxindolyl, oxiranyl (oxyranyl), oxybenzoisothiazolyl, oxy-alkenyl, oxyisoquinolyl, oxy-quinolinyl, oxathiolanyl (oxythiolanyl), phenanthridinyl (phenanthrinyl), phenanthrolinyl (phenanthrinyl), phenazinyl, phenothiazinyl, phenanthrenyl (benzothiofuranyl), phenanthrenyl>Thienyl (phenoxathiinyl), phenanthryl->Oxazinyl, phthalazinyl, phthalazinonyl (phthalazolyl), phthalazinonyl, benzopyrrolonyl (phtalimidyl), piperazinyl, piperidinyl, piperidonyl (e.g., 4-piperidonyl), pteridinyl (pteridinyl), purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolopyrimidinyl, pyrazolyl, pyridazinyl, pyridinyl, pyridopyrazinyl, pyridopyrimidinyl, pyridinyl, pyrimidinyl (pyrimidyl), pyronyl (pyrronyl), pyrrolidinyl, pyrrolonyl (e.g., 2-pyrrolidone), pyrrolinyl, pyrrolizidinyl (pyrrosizinyl), pyrrolyl (e.g., 2H-pyrrolyl), pyranyl>Quinazolinyl, quinolinyl, quinolizinyl (e.g., 4H-quinolizinyl), quinoxalinyl, quinuclidinyl, selenazinyl (selenazinyl), selenazolyl, selenophenyl (selen-ophelyl), succinimidyl (succininimidyl), sulfolane (sulfolanyl), tetrahydrofuranyl (tetrahydrofuranyl), tetrahydroisoquinolyl (tetrahydroisoquinolyl), tetrahydropyridinyl (tetrahydroisoquinolyl) tetrahydropyridinyl (piperidinyl), tetrahydropyranyl, tetrahydropyranonyl, tetrahydroquinolinyl (tetrahydroquinolinyl), tetrahydrothiophenyl, tetrazinyl, tetrazolyl, thiadiazinyl (e.g., 6H-1,2, 5-thiadiazinyl or 2H, 6H-1, 5, 2-dithiazinyl), thiadiazolyl, thianthrenyl (thianthrenyl), tetrahydrothiopyranyl (thianyl), thiaindenyl, thiaaza >A group, a thiazinyl group, a thiazolidinedione group (thiozolidinyl), a thiazolidinyl group, a thiazolyl group, a thienyl group, a thiepanyl group (thiepanyl group), a thiepanyl group, a thietanyl group (thietanyl group), a thietanyl group (thietyl group), a thietanyl group (thietanyl group), a thietanyl group (thiecanyl group), a thiochromanone group, a thiochroman group, a thiadiazinyl group, a thiadiazolyl group, a thioindoxyl group (thiomorpholinyl group), a thiomorpholinyl group, a thiophenyl group, a thiopyranyl group (thio)pyryl), thiopyranonyl, thiatriazolyl, thiourezolyl, thiooxacyclohexyl (thioxanyl), thiooxapentadienyl (thioxolyl), thymidinyl, triazinyl, triazolyl, trithianyl, oxazinyl, urezolyl, urodinyl (uretidinyl), uretinyl (uretinyl), uracil yl (urecyl), ureido, xanthenyl, xanthinyl (xanthonyl), and the like, as well as modified forms thereof (e.g., including one or more oxo and/or amino groups) and salts thereof. The heterocyclyl group may be substituted or unsubstituted. For example, a heterocyclyl group may be substituted with one or more substituents, as described herein with respect to aryl.

"Heterocyclyl" refers to the divalent form of heterocyclyl groups as described herein. In one instance, the heterocyclyldiyl is formed by removal of hydrogen from the heterocyclyl group. Exemplary heterocyclodiyl groups include piperidinyl, quinolinediyl, and the like. The heterocyclodiyl group may also be substituted or unsubstituted. For example, a heterocyclodiyl group may be substituted with one or more substituents as described herein for the heterocyclyl group.

"hydroxy" refers to an-OH group.

"hydroxyalkyl" refers to an alkyl group as defined herein substituted with one or more hydroxyl groups.

"hydroxyalkylene" refers to an alkylene group as defined herein substituted with one or more hydroxyl groups.

"nitro" means-NO ₂ A group.

"phosphate" refers to a group derived from phosphoric acid. One example of a phosphate group includes-O-P (=O) (OR) ^P1 )(OR ^P2 ) OR-O- [ P (=O) (OR) ^P1 )-O] _P3 -R ^P2 A group, wherein R is ^P1 And R is ^P2 Independently is H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl or optionally substituted arylalkylene, and wherein P3 is an integer from 1 to 5. Further examples of phosphates include orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, tetraphosphoric acid, trimetaphosphoric acid and/or phosphoric anhydride, or combinations thereof.

"phosphonates" or (phosphonates)"phosphonic acid" refers to-P (O) (OH) ₂ A group.

"spirocyclic group" refers to an alkylene diradical, both ends of which are bound to the same carbon atom of the parent group to form a spirocyclic group, and a heteroalkylene diradical, both ends of which are bound to the same atom. Non-limiting alkylene and heteroalkylene groups for use within the spirocyclic group include C _2-12 、C _2-11 、C _2-10 、C _2-9 、C _2-8 、C _2-7 、C _2-6 、C _2-5 、C _2-4 Or C _2-3 An alkylene group, C having one or more heteroatoms _1-12 、C _1-11 、C _1-10 、C _1-9 、C _1-8 、C _1-7 、C _1-6 、C _1-5 、C _1-4 、C _1-3 Or C _1-2 Heteroalkylene groups.

"sulfate" refers to a group derived from sulfuric acid. One example of a sulfate group includes-O-S (=O) ₂ (OR ^S1 ) A group, wherein R is ^S1 Is H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl or optionally substituted arylalkylene.

"sulfo" or "sulfonic acid" means-S (O) ₂ An OH group.

"sulfonyl" means-S (O) ₂ -or-S (O) ₂ R groups, wherein R may be H, optionally substituted alkyl or optionally substituted aryl. Non-limiting sulfonyl groups may include trifluoromethanesulfonyl groups (-SO) ₂ -CF ₃ Or Tf).

"thiocyanato" refers to the-SCN group.

"salt" refers to an ionic form of a compound or structure (e.g., any of the formulas, compounds, or compositions described herein) that includes a cationic or anionic compound to form a compound or structure that is electrically neutral. Salts are well known in the art. For example, non-toxic salts are described in Berge S M et al, "Pharmaceut ical sal ts," J.Pharm.Sci.1977, month 1, 66 (1): 1-19 and "Handbook of Pharmaceut ical Sal ts: properties, selection ion, and Use", wi ley-VCH, month 4 (2011) Two revisions, editors p.h.stahl and c.g.weruth. Salts may be prepared during the final isolation and purification of the compounds of the invention, either by reacting the free base groups with a suitable organic acid (thereby producing an anionic salt) or in situ by reacting the acid groups with a suitable metal or organic salt (thereby producing a cationic salt). Representative anionic salts include acetates, adipates, alginates, ascorbates, aspartate, benzenesulfonates, benzoates, bicarbonates, bisulphates, bitartrates, borates, bromides, butyrates, camphorates, camphorsulfonates, chlorides, citrates, cyclopentanepropionates, digluconates, dihydrochloride, biphosphates, dodecyl sulfate, ethylenediamine tetraacetate, ethanesulfonate, fumarate, glucoheptonate, gluconate, glutamate, glycerophosphate, hemisulfate, heptanoate, caproate, hydrobromide, hydrochloride, hydroiodide, hydroxyethanesulfonate, hydroxynaphthoates, iodides, lactates, lactobionate laurates, laurylsulfates, malates, maleates, malonates, mandelates, methanesulfonates, methyl bromide, methyl nitrate, methylsulfates, mucinates (mucate), 2-naphthalenesulfonates, nicotinates, nitrates, oleates, oxalates, palmates, pamoate, pectates, persulfates, 3-phenylpropionates, phosphates, picrates, pivalates, polygalacturonates, propionates, salicylates, stearates, hypoacetates, succinates, sulfates, tannates, tartrates, theophyllates (theophyllates), thiocyanates, triethyliodide, tosylate, undecanoates, valerates, and the like. Representative cationic salts include metal salts, such as alkali or alkaline earth salts, e.g., barium, calcium (e.g., calcium ethylenediamine tetraacetate), lithium, magnesium, potassium, sodium, and the like; other metal salts such as aluminum, bismuth, iron, and zinc; and nontoxic ammonium, quaternary ammonium and amine cations including, but not limited to, ammonium, tetramethyl ammonium, tetraethyl ammonium, methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, pyridine Etc. Other cationic salts include organic salts such as chloroprocaine, choline, dibenzylethylenediamine, diethanolamine, ethylenediamine, methylglucamine, and procaine. Other salts include ammonium, sulfonium, sulfoxonium, < >>Imine->ImidazoleBenzimidazole->Amidine->Guanidine->Phosphazene->Phosphazene->Pyridine->Etc., as well as other cationic groups described herein (e.g., optionally substituted iso +.>Azole->Optionally substituted->Azole->Optionally substituted thiazolyl>Optionally substituted pyrrole->Optionally substituted furans>Optionally substituted thiophenes->Optionally substituted imidazoles>Optionally substituted pyrazolesOptionally substituted isothiazole->Optionally substituted triazoles>Optionally substituted tetrazolium>Optionally substituted furazanOptionally substituted pyridines>Optionally substituted pyrimidines->Optionally substituted pyrazinyl->Optionally substituted triazines->Optionally substituted tetrazine->Optionally substituted pyridazine->Optionally substituted->Oxazine->Optionally substituted pyrrolidino>Optionally substituted pyrazolidino->Optionally substituted imidazoline->Optionally substituted Iso->Oxazolidine->Optionally substituted->AzolidinesOptionally substituted piperazine->Optionally substituted piperidines->Optionally substituted morpholino->Optionally substituted azepane->(azepanium), optionally substituted aza +.>(azepinium), optionally substituted indoles- >Optionally substituted isoindoles>Optionally substituted indolizine->Optionally substituted indazoles->Optionally substituted benzimidazoles->Optionally substituted isoquinolines->Optionally substituted quinolizine->Optionally substituted dehydroquinolizine>Optionally substituted quinolines->Optionally substituted isoindoles>Optionally substituted benzimidazoles->And optionally substituted purine->). Other salts may include anions such as halide (e.g., F ^– 、Cl ^– 、Br ^– Or I ^– ) Hydroxyl radical (e.g. OH ^– ) Borate (e.g. tetrafluoroborate (BF) ₄ ^– ) Carbonate (e.g. CO) ₃ ^2– Or HCO ₃ ^– ) Or sulfate radical (e.g. SO ₄ ^2– )。

"leaving group" refers to an atom (or group of atoms) having an electron withdrawing capability that can be displaced as a stable species while carrying a bonding electron, or that can be displaced by a substitution reaction. Examples of suitable leaving groups include H, halide, and sulfonate, including, but not limited to, triflate (-OTf), methanesulfonate (-OMs), toluenesulfonate (-OTs), p-bromophenylsulfonate (-OBs), acetate, cl, br, and I.

"attached," "attached," or related words means any covalent or non-covalent bonding interaction between two components. Non-covalent bonding interactions include, but are not limited to, hydrogen bonding, ionic interactions, halogen bonding, electrostatic interactions, pi-bonding interactions, hydrophobic interactions, inclusion complexes, clathration interactions, van der Waals interactions, and combinations thereof.

Detailed description of the preferred embodiments

The present disclosure relates to compositions comprising a first polymer structure and a second polymer structure, wherein at least one of these structures comprises an ionizable or ionic moiety. In some embodiments, both the first and second structures comprise ionizable or ionic moieties. In use, the first and second structures are different, thus forming a copolymer, polymer blend, or other multiphase polymer composition. The conduction of charge through the material may be controlled by the type and amount of charge provided by the ionizable/ionic moieties (e.g., anionic and/or cationic charge on the first and/or second structures).

The composition may include any combination of a first structure (e.g., one or more of formulas (I-V)) and a second structure (e.g., one or more of formulas (X) - (XXXIV)), as described herein. By using two different structures, the properties of the composition can be adjusted based on the selection of the first and second structures. Each of the first and second structures may independently comprise a polymer unit. The polymer units may be homopolymers, copolymers, block copolymers, or other useful combinations of repeating monomer units.

The composition may comprise a polymer unit selected from the first structure (e.g., any of those described herein, e.g., one or more of formulas (I-V)). For example, the composition may include a plurality of first structures, wherein each first structure is the same (e.g., each Ar, R ⁷ -R ¹⁰ And rings a-c (if present) are the same in each monomer unit). In another instance, the composition can include a plurality of first structures, wherein at least two of the first structures are different (e.g., ar, R ⁷ -R ¹⁰ And at least one of the rings a-c (if present) differs between the two monomer units. Thus, even if the composition includes only polymer units characterized by the first structure, the composition may be a homopolymer, copolymer, block copolymer, or other useful combination of repeating monomer units.

Thus, in one embodiment, the composition comprises a plurality of first structures, wherein:

(i) The first structure is selected from the following:

or a salt thereof, wherein:

R ⁷ and R is ⁸ Each of which is independently an electron withdrawing moiety, H, an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted heteroaliphatic group, an optionally substituted heteroalkyl group, an optionally substituted aromatic group, an optionally substituted aryl group, or an optionally substituted arylalkylene group, wherein R ⁷ Or R is ⁸ At least one of which comprises an electron withdrawing moiety or wherein R ⁷ And R is ⁸ May together form an optionally substituted cyclic group;

R ⁹ and R is ¹⁰ Each of which is independently H, an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted heteroaliphatic group, an optionally substituted heteroalkyl group, an optionally substituted aromatic group, an optionally substituted aryl group, or an optionally substituted arylalkylene group, or wherein R ⁹ Or R is ¹⁰ May together form an optionally substituted cyclic group;

ar comprises or is optionally substituted arylene;

n is an integer of 1 or more;

each of ring a, ring b, and/or ring c may be optionally substituted; and

wherein rings a-c, R ⁷ 、R ⁸ 、R ⁹ And R is ¹⁰ Optionally comprising an ionizable or ionic moiety.

In some embodiments, each of the first structures is the same. In other embodiments, at least two of the first structures are different (e.g., wherein the composition comprises a copolymer).

The compositions herein may include any useful combination of repeating monomer units. In one instance, the composition may include-A-A-a-or- [ a ] -, where a represents monomer units and [ a ] represents a block comprising only a monomer units. A may be selected from those provided as the first or second structure.

In another instance, the composition includes- [ A ] - [ A-combination-B ] - [ B ] -, where A and B represent different monomer units. [A] And [ B ] represents a polymer block comprising only A monomer units and only B monomer units, respectively. The [ A-combination-B ] block means a block comprising some combination of A and B monomer units. Each of a and B may be selected from those provided as the first and/or second structures. In some embodiments, both A and B are of a first structure (e.g., selected from formulas (I-V)). In other embodiments, a is a first structure (e.g., selected from formulas (I-V)), and B is a second structure (e.g., selected from formulas (X) - (XXXIV)).

In another case, the composition comprises at least one alternating/periodic block, wherein the different monomers have an ordered sequence, such as- [ ase:Sub>A-B-ase:Sub>A-B ] -, - [ ase:Sub>A-B-C-ase:Sub>A-B-C ] -, - [ ase:Sub>A-ase:Sub>A-B ] -, ase:Sub>A-ase:Sub>A-B- ] -, ase:Sub>A-B-C; - [ ase:Sub>A-ase:Sub>A-B- ] -, ase:Sub>A- [ ase:Sub>A-B-ase:Sub>A-ase:Sub>A-ase:Sub>A-B- ] -and the like. A. B and C represent different monomer units. The brackets examples represent polymer blocks in which the monomer sequence is repeated throughout the block. A. Each of B and C may be selected from those provided as the first and/or second structures (e.g., each of A, B and C includes or is independently a structure of formulae (I) - (V) or (X) - (XXXIV)). In some embodiments, each of A, B and C is a first structure (e.g., selected from formula (I-V)). In other embodiments, A is a first structure (e.g., selected from formulas (I-V)), B is a second structure (e.g., selected from formulas (X) - (XXXIV)), and C is a first or second structure (e.g., selected from formulas (I-V) or (X) - (XXXIV)).

In yet another instance, the composition includes specific units covalently bonded between at least a pair of blocks, such as [ A ] -D [ B ] or [ A ] -D [ B ] - [ C ], wherein D can be a monomer unit or a linking moiety (e.g., any of those described herein). More than one D may be present, for example in [ A ] -D-D-B ] or [ A ] -D-D-D-B ], where each C may be the same or different. [A] Represents a block comprising only a monomer units; [B] represents a block comprising only B monomer units; [C] represents a block comprising only C monomer units; and D may represent a single monomer unit (e.g., any of those described herein) or a linking moiety (any of those described herein). A. Each of B and C may be selected from those provided as the first and/or second structures (e.g., each of A, B and C includes or is independently a structure of formulae (I) - (V) or (X) - (XXXIV)). D may be selected from those provided as a first and/or second structure (e.g., selected from formulas (I) - (V) or (X) - (XXXIV)) or as a linking moiety (e.g., L).

The compositions herein also encompass other alternative constructions, such as branched constructions, diblock copolymers, triblock copolymers, random or statistical copolymers, stereo block copolymers, gradient copolymers, graft copolymers, and combinations of any of the blocks or regions described herein.

The compositions herein may be characterized by a first Molecular Weight (MW) of a first structure (e.g., as a polymer unit), a second MW of a second structure (e.g., as a polymer unit), or the total MW of the composition. In one embodiment, the first MW, the second MW, or the total M is a weight average molecular weight (Mw) of at least 10,000g/mol, at least 20,000g/mol, or at least 50,000 g/mol; or about 5,000 to 2,500,000g/mol, for example 10,000 to 2,500,000g/mol,50,000 to 2,500,000g/mol,10,000 to 250,000g/mol,20,000 to 250,000g/mol, or 20,000 to 200,000g/mol. In another embodiment, the first MW, the second MW, or the total MW is a number average molecular weight (Mn) of at least 20,000g/mol or at least 40,000 g/mol; or about 2,000 to 2,500,000g/mol, for example 5,000 to 750,000g/mol or 10,000 to 400,000g/mol.

The composition may include any useful number of monomer units n, m1, m2, m3, or m 4. non-limiting examples of each of n, m1, m2, m3, and m4 are independently 1 or greater, 20 or greater, 50 or greater, 100 or greater, and 1-1,000,000, for example 10-1,000,000, 100-1,000,000, 200-1,000,000, 500-1,000,000, or 1,000-1,000,000.

First structure

Within the composition, the first structure may comprise polymeric units, which in turn may comprise one or more ionizable or ionic moieties. In non-limiting embodiments, the polymer units can have an arylene-containing backbone that provides an organic framework through which ionizable/ionic moieties can be added.

The arylene-containing backbone may also provide aromatic groups that facilitate the addition of reactive carbocations (e.g., by reaction with friedel-crafts alkylating agents). In this way, monomer units having aromatic groups can be reacted together to form polymer units. Such addition/polymerization reactions may be promoted in any useful manner, for example, by including electron withdrawing groups in the vicinity of the carbocation. Thus, in some non-limiting cases, the first structure can include an optionally substituted aromatic group and an electron withdrawing group.

The reactive carbocations may also provide functional groups that may be further modified. For example, the reactive carbocation may be associated with-L ^A -RG group is attached, wherein L ^A Is a linking moiety (e.g., any of the herein) and RG is a reactive group (e.g., halo). Upon addition of carbocations and-L to the polymer units ^A After the RG group, the RG group may be further reacted with an ionizable reagent (e.g., amine, NR ^N1 R ^N2 R ^N3 ) To provide ionic moieties (e.g., ammonium, -N ⁺ R ^N1 R ^N2 R ^N3 )。

Thus, in some non-limiting embodiments, the first structure comprises a polymer unit (e.g., any of the herein described) having an ionizable/ionic moiety and an electron withdrawing group. In some cases, the polymer units are formed by using one or more monomer units. Non-limiting monomer units may include one or more of the following:

wherein Ar is an optionally substituted arylene or an optionally substituted aromatic group; ak is optionally substituted alkylene, optionally substituted haloalkylene, optionally substituted heteroalkylene, optionally substituted aliphatic or optionally substituted heteroaliphatic; and L is a linking moiety (e.g., any of those described herein) or can be-C (R ⁷ )(R ⁸ ) - (e.g. for any R described herein) ⁷ And R is ⁸ A group). In particular examples, ar, L, and/or Ak may be optionally substituted with one or more ionizable or ionic moieties and/or one or more electron withdrawing groups.

In some embodiments, the first structure comprises a polymer unit selected from the group consisting of:

and salts thereof, wherein:

ar comprises or is an optionally substituted aromatic group or an optionally substituted arylene group (any of those described herein);

each n is independently an integer of 1 or more;

each of ring a, ring b, and/or ring c may be optionally substituted; and

wherein rings a-c, R ⁷ And R is ⁸ Optionally including an ionizable or ionic moiety.

For ring a, ring b, ring c, R ⁷ And R is ⁸ Additional substituents may include one or more optionally substituted arylene groups, as well as any of the alkyl or aryl groups described herein. Non-limiting examples of Ar include, for example, phenylene (e.g., 1, 4-phenylene, 1, 3-phenylene, etc.), biphenylene (e.g., 4 '-biphenylene, 3' -biphenylene, 3,4 '-biphenylene, etc.), terphenylene (e.g., 4' -terphenylene), triphenylene, diphenyl ether, anthracene (e.g., 9, 10-anthracene), naphthalene (e.g., 1, 5-naphthalene, 1, 4-naphthalene, 2, 6-naphthalene, 2, 7-naphthalene, etc.), tetrafluorophenylene (e.g., 1, 4-tetrafluorophenylene, 1, 3-tetrafluorophenylene), etc., as well as others described herein.

The first structure may include a polymer unit having an electron withdrawing moiety and a fluorenyl-based backbone. For example, the first structure may comprise the following polymer units:

Or a salt thereof, wherein:

n is independently an integer of 1 or more;

each of ring a, ring b, and/or ring c may be optionally substituted; and

wherein rings a-b, R ⁷ 、R ⁸ 、R ⁹ And R is ¹⁰ Optionally including an ionizable or ionic moiety.

In particular embodiments, R ⁹ And R is ¹⁰ Independently including an ionizable/ionic moiety.

In some embodiments (e.g., formulas (I) - (V)), ring a, ring b, and/or ring c comprise an ionizable or ionic moiety. In other embodiments, R ⁸ Including an ionizable or ionic moiety. In particular embodiments, the ionic moiety comprises or is-L ^A -X ^A Wherein L is ^A Is a linking moiety (e.g., an optionally substituted aliphatic, alkylene, heteroaliphatic, heteroalkylene, aromatic, or arylene group); and X ^A Is an acidic moiety, a basic moiety, a multi-ionic moiety, a cationic moiety, or an anionic moiety. X is X ^A Non-limiting examples of (a) include amino, ammonium cation, heterocyclic cation, piperidineCation, azepane->Cation, & lt/EN & gt>Cation, phosphazene->Cations or others herein.

In other embodiments (e.g., of formulae (I) - (V)), R ⁷ Comprising an electron withdrawing moiety. Non-limiting electron withdrawing moieties can include OR be optionally substituted haloalkyl, cyano (CN), phosphate (e.g., -O (p=o) (OR) ^P1 )(OR ^P2 ) OR-O- [ P (=O) (OR) ^P1 )-O] _P3 -R ^P2 ) Sulfate ester group (e.g. -O-S (=O) ₂ (OR ^S1 ) Sulfonic acid group (-SO) ₃ H) Sulfonyl groups (e.g. -SO) ₂ -CF ₃ ) Difluoroborane (-BF) ₂ ) Dihydroxyboron (-B (OH)) ₂ ) Thiocyanato (-SCN) or piperidineIn further embodiments, R ⁷ Comprising electron withdrawing moieties and R ⁸ Including ionizable/ionic moieties. Other non-limiting phosphate groups may comprise derivatives of phosphoric acid, such as orthophosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, trimetaphosphoric acid, and/or phosphoric anhydride, or combinations thereof.

In some embodiments (e.g., for any of the structures herein, e.g., in formulas (I) - (V)), R ⁷ Including optionally substituted aliphatic groups. In one embodiment, R ⁷ Including optional alkyl groups.

In other embodiments (e.g., for any of the structures hereinIn the formulae (I) - (V), for example, R ⁸ Including optionally substituted aliphatic groups or optionally substituted heteroaliphatic groups. In a particular embodiment, the aliphatic or heteroaliphatic group is substituted with an oxo group (=o) or an oxime group (=n-OH). In one embodiment, R ⁸ is-C (=X) -R ^8’ Wherein X is O or N-OH; and R is ^8’ Is an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted heteroaliphatic group, an optionally substituted heteroalkyl group, an optionally substituted alkoxy group, an optionally substituted haloalkyl group, or an optionally substituted alkanoyl group.

In other embodiments (e.g., for any of the structures herein, e.g., in formulas (I) - (V)), R ⁷ And R is ⁸ Together forming an optionally substituted cyclic group. For example, R ⁷ And R is ⁸ May together form an optionally substituted spirocyclic group, as defined herein. In certain embodiments, the spirocyclic groups are independently substituted with one or more ionizable or ionic moieties (e.g., any of those described herein). In some embodiments, formulas (I) - (V) may be represented as follows:

Or a salt thereof, wherein R ^7’ And R is ^8’ Together forming an optionally substituted alkylene group or an optionally substituted heteroalkylene group. In certain embodiments, the optionally substituted alkylene group or the optionally substituted heteroalkylene group is independently substituted with one or more ionizable or ionic moieties.

In addition, non-limiting polymer units may include structures of any one or more of the following:

or a salt thereof, wherein:

n is from 1 or greater;

each L ^8A 、L ^B’ And L ^B” Independently a linking moiety; and

each X is ^8A 、X ^8A’ 、X ^8A” 、X ^B’ And X ^B” Independently an acidic moiety or a basic moiety.

In any embodiment herein, ring a, ring b, ring c, ak, R ⁷ 、R ⁸ 、R ⁹ And R is ¹⁰ An ionizable or ionic moiety may optionally be included. In addition, ring a, ring b, ring c, R ⁷ 、R ⁸ 、R ⁹ And R is ¹⁰ May include one or more optionally substituted arylene groups.

In any of the embodiments herein, the electron withdrawing moiety can be an optionally substituted haloalkyl (e.g., C _1-6 Haloalkyl groups including halomethyl, perhalomethyl, haloethyl, perhaloethyl, and the like), cyano groups (CN), phosphate groups (e.g., -O (P=O) (OR) ^P1 )(OR ^P2 ) OR-O- [ P (=O) (OR) ^P1 )-O] _P3 -R ^P2 ) Sulfate ester group (e.g. -O-S (=O) ₂ (OR ^S1 ) Sulfonic acid group (-SO) ₃ H) Sulfonyl groups (e.g. -SO) ₂ -CF ₃ ) Difluoroborane (-BF) ₂ ) Dihydroxyboron (-B (OH)) ₂ ) Thiocyanato (-SCN) or piperidineOther non-limiting phosphate groups may comprise derivatives of phosphoric acid, such as orthophosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, trimetaphosphoric acid, and/or phosphoric anhydride, or combinations thereof.

In some embodiments (e.g., for any of the herein described, e.g., in formulas (I) - (V)), the non-limiting haloalkyl group comprises a fluoroalkyl group (e.g., -C _x F _y H _z ) Perfluoroalkyl (e.g. -C) _x F _y ) Chloroalkyl (example)Such as-C _x Cl _y H _z ) Perchloroalkyl radicals (e.g. -C) _x Cl _y ) Bromoalkyl (e.g. -C) _x Br _y H _z ) Full bromoalkyl (e.g. -C) _x Br _y ) Iodinated alkyl groups (e.g. -C) _x I _y H _z ) Or a periodate group (e.g. -C _x I _y ). In some embodiments, x is 1-6, y is 1-13 and z is 0-12. In a particular embodiment, z=2x+1-y. In other embodiments, x is 1-6, y is 3-13 and z is 0 (e.g., sum y=2x+1).

The polymer unit may include one or more substituents to the ring portion (e.g., as provided by an aromatic or arylene group) or the linear portion (e.g., as provided by an aliphatic or alkylene group) of the unit. Non-limiting substituents may include lower unsubstituted alkyl (e.g., C _1-6 Alkyl), lower substituted alkyl (e.g., optionally substituted C) _1-6 Alkyl), lower haloalkyl (e.g. C _1-6 Haloalkyl), halo (e.g., F, cl, br, or I), unsubstituted aryl (e.g., phenyl), halo-substituted aryl (e.g., 4-fluoro-phenyl), substituted aryl (e.g., substituted phenyl), and others.

Second structure

The second structure is generally different from the first structure but may also include polymer units. In use, the first and second structures together can provide a composition having beneficial chemical and physical properties, such as beneficial Ion Exchange Capacity (IEC), ionic conductivity, water absorption, degree of swelling, specific conductivity, mechanical stability, and the like.

Selection of particular polymer components (e.g., first structure, second structure, polymer units, ionic moieties, cross-linked structures, etc.) can provide useful properties to the composition. In one instance, the polymer component may be selected to minimize water absorption, where excess water may result in flooding of the electrochemical cell. In another case, the polymer component may be selected to provide softening or plasticizing resistance. In other embodiments, the composition may be an ion conducting polymer having a specific conductivity greater than about 1mS/cm for anions and/or cations.

In one embodiment, the second structure may include one or more of the following: optionally substituted aliphatic, optionally substituted alkylene, optionally substituted aromatic, optionally substituted arylene, optionally substituted haloalkylene, optionally substituted alkyleneoxy, optionally substituted aryleneoxy, optionally substituted phosphazene (e.g., -P (R ^P1 R ^P2 ) =n-) and combinations thereof.

The second structure may include a polymer unit formed by using one or more of the following monomer units:

wherein Ar is an optionally substituted arylene or an optionally substituted aromatic group; ak is optionally substituted alkylene, optionally substituted haloalkylene, optionally substituted aliphatic, optionally substituted heteroalkylene, or optionally substituted heteroaliphatic; l is a linking moiety (e.g., any of those described herein); and Ar, L or Ak may be optionally substituted with one or more ionizable or ionic moieties. Non-limiting examples of Ar include, for example, phenylene (e.g., 1, 4-phenylene, 1, 3-phenylene, etc.), biphenylene (e.g., 4 '-biphenylene, 3' -biphenylene, 3,4 '-biphenylene, etc.), terphenylene (e.g., 4' -terphenylene), triphenylene, diphenyl ether, anthracene (e.g., 9, 10-anthracene), naphthalene (e.g., 1, 5-naphthalene, 1, 4-naphthalene, 2, 6-naphthalene, 2, 7-naphthalene, etc.), tetrafluorophenylene (e.g., 1, 4-tetrafluorophenylene, 1, 3-tetrafluorophenylene), etc., as well as others described herein.

Any portion of the second structure may optionally include an ionizable or ionic moiety. In particular embodiments, the ionic moiety comprises or is-L ^A -X ^A Wherein L is ^A Is a linking moiety (e.g., an optionally substituted aliphatic, alkylene, heteroaliphatic, heteroalkylene, aromatic, or arylene group); and X ^A Is an acidic moiety, a basic moiety, a multi-ionic moiety, a cationic moiety, or an anionic moiety. X is X ^A Non-limiting examples of (a) include amino, ammonium cation, heterocycleCation(s),Cation, phosphazene->Cations or others herein.

The second structure may include other polymer units having cyclic cationic groups. For example, the second structure may comprise a polymer unit selected from the group consisting of:

or a salt thereof, wherein:

n is an integer of 1 or more;

q is 0, 1, 2 or greater;

each of rings a-c may be optionally substituted; and

wherein rings a-c, R ⁹ And R is ¹⁰ Optionally including an ionizable or ionic moiety.

In other embodiments (e.g., for any of the structures herein, e.g., in formulas (X) - (XI)), R ⁹ And R is ¹⁰ Together forming an optionally substituted cyclic group. For example, R ⁹ And R is ¹⁰ May together form an optionally substituted spirocyclic group, as defined herein. In certain embodiments, the spirocyclic groups are independently substituted with one or more ionizable or ionic moieties (e.g., any of those described herein). In some embodiments, formulas (X) - (XI) may be represented as follows:

salts thereof, wherein R ^9’ And R is ^10’ Together forming an optionally substituted alkylene group or an optionally substituted heteroalkylene group. In certain embodiments, the optionally substituted alkylene group or the optionally substituted heteroalkylene group is independently substituted with one or more ionizable or ionic moieties. In other embodiments, the optionally substituted alkylene group or the optionally substituted heteroalkylene group is independently substituted with one or more aliphatic or alkyl groups. Without wishing to be bound by a mechanism, substitution of alkylene or heteroalkylene groups to provide bulky substituents may protect the cationic nitrogen moiety from degradation.

The second structure may comprise a combination of soft and hard segments. For example, the second structure may comprise the following polymer units:

or a salt thereof, wherein:

R ⁷ and R is ⁸ Each of which is independently an electron withdrawing moiety, H, an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted heteroaliphatic group, an optionally substituted heteroalkyl group, an optionally substituted aromatic group, an optionally substituted aryl group, or an optionally substituted arylalkylene group, wherein R ⁷ Or R is ⁸ Comprises an electron withdrawing moiety;

each Ak is optionally substituted alkylene;

each of n1, n2, n3, and n4 is independently an integer of 1 or more;

each of ring a or ring b may be optionally substituted; and

wherein rings a-b, R ⁷ And R is ⁸ Optionally comprising an ionizable or ionic moiety.

In some embodiments (e.g., for any of the structures herein, e.g., in formula (XI I)), R ⁷ Including optionally substituted aliphatic groups. In one embodiment, R ⁷ Including optional alkyl groups.

In some embodiments (e.g., for any of the structures herein, e.g., in formula (XI I)), the electron withdrawing moiety is a haloalkyl group. Non-limiting haloalkyl groups include fluoroalkyl groups (e.g., -C _x F _y H _z ) Perfluoroalkyl (e.g. -C) _x F _y ) Chloroalkyl (e.g. -C) _x Cl _y H _z ) Perchloroalkyl radicals (e.g. -C) _x Cl _y ) Bromoalkyl (e.g. -C) _x Br _y H _z ) Full bromoalkyl (e.g. -C) _x Br _y ) Iodinated alkyl groups (e.g. -C) _x I _y H _z ) Or a periodate group (e.g. -C _x I _y ). In some embodiments, x is 1-6, y is 1-13 and z is 0-12. In a particular embodiment, z=2x+1-y. In other embodiments, x is 1-6, y is 3-13 and z is 0 (e.g., sum y=2x+1).

The second structure may include a polyphenylene. For example, the second structure may comprise the following polymer units:

or a salt thereof, wherein:

m is an integer of 1 or more; and

each of rings a-i may be optionally substituted and/or may optionally include an ionizable or ionic moiety.

In particular embodiments, an ionizable/ionic moiety is present on one or more of the loops a, b, f, g, h or i. In some embodiments, the ionic moiety comprises or is-L ^A -X ^A Wherein L is ^A Is a linking moiety (e.g., an optionally substituted aliphatic, alkylene, heteroaliphatic, or heteroalkylene); and X ^A Is an acidic structural part, a basic structural part or a plurality ofAn ionic moiety, a cationic moiety, or an anionic moiety (e.g., including amino, ammonium, heterocyclic, or others herein).

The second structure may comprise polybenzimidazole optionally in combination with other arylene-containing monomer units. In one instance, the second structure may comprise a polymer unit selected from the group consisting of:

(XV) or a salt thereof, wherein:

each L is independently a linking moiety;

m is an integer of 1 or more; and

each of rings a-f may be optionally substituted and/or may optionally include an ionizable or ionic moiety.

In certain embodiments, each nitrogen atom on ring a and/or b is substituted with an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted aromatic group, an optionally substituted aryl group, an ionizable moiety, or an ionic moiety. In other embodiments, one nitrogen atom of each of rings a and/or b is substituted with an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted aromatic group, an optionally substituted aryl group, an ionizable moiety, or an ionic moiety. In particular embodiments, the ionic moiety comprises or is-L ^A -X ^A Wherein L is ^A Is a linking moiety (e.g., an optionally substituted aliphatic, alkylene, or heteroaliphatic group, e.g., C _1-12 、C _3-12 、C _4-12 Or C _6-12 Form (c); and X ^A Is an acidic moiety, a basic moiety, a multi-ionic moiety, a cationic moiety, or an anionic moiety (e.g., amino, ammonium cation, heterocyclic cation, or others herein).

In other embodiments, the linking moiety (e.g., L) is a covalent bond, -O-, -SO ₂ -, -C (O) -, optionally substituted aliphatic, optionally substituted alkyleneRadicals (e.g. -CR ₂ -wherein R is H, alkyl or haloalkyl), optionally substituted haloalkylene or any other linking moiety described herein.

Other second structures include those having multiple arylene groups. In some embodiments, the second structure comprises a polymer unit selected from the group consisting of:

or a salt thereof, wherein:

L ¹ 、L ² 、L ³ and L ⁴ Independently a linking moiety;

m is an integer of 1 or more; and

each of rings a-e may be optionally substituted and/or may optionally include an ionizable or ionic moiety.

In certain embodiments, at least one of rings a-e is substituted with an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted aromatic group, an optionally substituted aryl group, an ionizable moiety, or an ionic moiety. In some embodiments, at least ring a is substituted with an ionizable or ionic moiety. In particular embodiments, the ionic moiety comprises or is-L ^A -X ^A Wherein L is ^A Is a linking moiety (e.g. optionally substituted aliphatic, alkylene, heteroaliphatic or heteroalkylene, e.g. C _1-12 、C _1-6 、C _4-12 Or C _6-12 Form (c); and X ^A Is an acidic moiety, a basic moiety, a multi-ionic moiety, a cationic moiety, or an anionic moiety (e.g., amino, ammonium cation, heterocyclic cation, or others herein).

In some embodiments, the linking moiety (e.g., L ¹ 、L ² 、L ³ Or L ⁴ ) Is a covalent bond, -O-, -SO ₂ -, -C (O) -, an optionally substituted aliphatic group, an optionally substituted alkylene group (e.g. -CR ₂ -，Wherein R is H, alkyl or haloalkyl), optionally substituted haloalkylene, optionally substituted alkyleneoxy, optionally substituted heteroaliphatic, optionally substituted heteroalkylene, or any other linking moiety described herein.

Segments of arylene-containing groups may also be used. For example, the second structure may comprise the following polymer units:

or a salt thereof, wherein:

L ¹ 、L ² and L ³ Independently a linking moiety;

each of m1, m2, and m3 is independently an integer of 1 or more; and

each of rings a-c may be optionally substituted and/or may optionally include an ionizable or ionic moiety.

In certain embodiments, at least one of rings a-c is substituted with a halo, an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted aromatic group, an optionally substituted aryl group, an ionizable moiety, or an ionic moiety. In some embodiments, at least one of rings a-c is substituted with both halo and optionally substituted alkyl. In other embodiments, at least one of rings a-c is substituted with both an optionally substituted alkyl group and an ionizable/ionic moiety. In particular embodiments, the ionic moiety comprises or is-L ^A -X ^A Wherein L is ^A Is a linking moiety (e.g. optionally substituted aliphatic, alkylene, heteroaliphatic or heteroalkylene, e.g. C _1-12 、C _1-6 、C _4-12 Or C _6-12 Form (c); and X ^A Is an acidic moiety, a basic moiety, a multi-ionic moiety, a cationic moiety, or an anionic moiety (e.g., amino, ammonium cation, heterocyclic cation, or others herein).

In other embodiments, the linking moiety (e.g., L ¹ 、L ² Or L ³ ) Is a covalent bond, -O-, -SO ₂ -, -C (O) -, optionally substituted alkylene (e.g. -CR) ₂ -, wherein R is H, alkyl, or haloalkyl) or any other linking moiety described herein. In other embodiments, each linking moiety (e.g., L ¹ 、L ² Or L ³ ) is-O-.

The second structure may comprise halogenated polymer units. In some embodiments, the second structure comprises the following polymer units:

wherein m is an integer of 1 or more. In some embodiments, one or more hydrogen or fluorine atoms may be substituted to include an ionizable or ionic moiety. In particular embodiments, the ionic moiety comprises or is-L ^A -X ^A or-L ^A -CH(-L ^A’ -X ^A ) -, wherein L ^A And L ^A’ Independently a linking moiety (e.g., an optionally substituted aliphatic group, alkylene, heteroaliphatic group, heteroalkylene, aromatic group, arylene, or-Ar-L-, wherein Ar is an optionally substituted arylene and Ak is an optionally substituted alkylene); and X ^A Is an acidic moiety, a basic moiety, a multi-ionic moiety, a cationic moiety, or an anionic moiety (e.g., amino, ammonium cation, heterocyclic cation, or others herein).

In other embodiments, the second structure comprises a polymer unit selected from the group consisting of:

or a salt thereof, wherein:

R ¹ and R is ² Independently is an electron withdrawing moiety, H, an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted heteroaliphatic group, an optionally substituted heteroalkyl group, an optionally substituted aromatic group, an optionally substituted aryl group, or an optionally substituted arylalkylene group;

L ¹ 、L ² 、L ³ And L ⁴ Independently a linking moiety;

each of m1 and m2 is independently an integer of 1 or more; and

ring a may be optionally substituted and/or may optionally contain an ionizable or ionic moiety.

In certain embodiments, ring a is substituted with a halo, an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted aromatic group, an optionally substituted aryl group, an ionizable moiety, or an ionic moiety. In some embodiments, at least one of ring a is substituted with both an optionally substituted alkyl group and an ionizable/ionic moiety. In particular embodiments, the ionic moiety comprises or is-L ^A -X ^A Wherein L is ^A Is a linking moiety (e.g., an optionally substituted aliphatic, alkylene, heteroaliphatic, or heteroalkylene); and X ^A Is an acidic moiety, a basic moiety, a multi-ionic moiety, a cationic moiety, or an anionic moiety (e.g., amino, ammonium cation, heterocyclic cation, or others herein).

In other embodiments, the linking moiety (e.g., L ¹ 、L ² 、L ³ Or L ⁴ ) Is a covalent bond, -O-, -SO ₂ -, -C (O) -, optionally substituted alkylene (e.g. -CR) ₂ -wherein R is H, alkyl or haloalkyl), optionally substituted haloalkylene or any other linking moiety described herein. In particular embodiments, R ² Is H; and L ² And L ³ Independently is a covalent bond, an optionally substituted alkylene group, or an optionally substituted alkyleneoxy group. L (L) ¹ May be an optionally substituted alkylene or an optionally substituted haloalkylene. L (L) ⁴ And (if present) may be a covalent bond, -O-, and optionallySubstituted alkylene or optionally substituted alkyleneoxy.

The second structure may comprise epoxide-derived or vinyl alcohol-derived polymer units. In some embodiments, the second structure comprises a polymer unit selected from the group consisting of:

or a salt thereof, wherein:

R ¹ and R is ⁸ Independently is an electron withdrawing moiety, H, an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted heteroaliphatic group, an optionally substituted heteroalkyl group, an optionally substituted aromatic group, an optionally substituted aryl group, or an optionally substituted arylalkylene group;

L ¹ 、L ² and L ³ Independently a linking moiety; and

each m is independently an integer of 1 or more;

wherein R is ⁸ An ionizable or ionic moiety may optionally be included.

In particular embodiments, R ⁸ And/or the ionic moiety comprises or is-L ^A -X ^A Wherein L is ^A And L ^A’ Independently a linking moiety (e.g., an optionally substituted aliphatic group, alkylene group, heteroaliphatic group, heteroalkylene group, aromatic group, or arylene group); and X ^A Is an acidic moiety, a basic moiety, a multi-ionic moiety, a cationic moiety, or an anionic moiety (e.g., amino, ammonium cation, heterocyclic cation, or others herein).

In some embodiments, R ¹ Is H; and L ¹ Including covalent bonds, -O-, -C (O) -, optionally substituted alkylene, or optionally substituted heteroalkylene. In some embodiments, R ⁸ Including an ionizable or ionic moiety. In other embodiments, L ² And L ³ Each of which is independently a covalent bond, -O-,Optionally substituted alkylene or optionally substituted heteroalkylene.

In some embodiments, the second structure comprises the following polymer units:

or a salt thereof, wherein:

L ¹ 、L ² 、L ³ and L ⁴ Independently a linking moiety; and

each of m1, m2, and m3 is independently an integer of 1 or more.

In particular embodiments, the oxygen atom present in the second structure may be mixed with a base dopant (e.g., K ⁺ ) And (5) associating. In other embodiments, the linking moiety (e.g., L ¹ 、L ² 、L ³ Or L ⁴ ) Is optionally substituted alkylene (e.g. -CR ₂ -wherein R is H, alkyl or haloalkyl), optionally substituted hydroxyalkylene or any other linking moiety described herein.

The second structure may comprise a phosphazene-based polymer. In some embodiments, the second structure comprises the following polymer units:

or a salt thereof, wherein:

R ¹ 、R ² 、R ³ and R is ⁸ Each of which is independently an electron withdrawing moiety, H, an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted heteroaliphatic group, an optionallyA substituted heteroalkyl, an optionally substituted aromatic group, an optionally substituted aryl, an optionally substituted aryloxy, or an optionally substituted arylalkylene group;

L ¹ 、L ² 、L ³ and L ⁴ Independently a linking moiety; and

each of m1 and m2 is independently an integer of 1 or more.

Wherein R is ⁸ An ionizable or ionic moiety may optionally be included.

In particular embodiments, R ⁸ And/or the ionic moiety comprises or is-L ^A -X ^A Wherein L is ^A Is a linking moiety (e.g., an optionally substituted aliphatic, alkylene, heteroaliphatic, heteroalkylene, aromatic, or arylene group); and X ^A Is an acidic moiety, a basic moiety, a multi-ionic moiety, a cationic moiety or an anionic moiety (e.g., heterocyclic cation,Cation, phosphazene->Cations or others herein).

In some embodiments, R ¹ 、R ² And R is ³ Is an optionally substituted aromatic group, an optionally substituted aryl group, an optionally substituted aryloxy group, or an optionally substituted arylalkylene group. In other embodiments, the linking moiety (e.g., L ¹ 、L ² 、L ³ Or L ⁴ ) Is a covalent bond, -O-, -SO ₂ -, -C (O) -, optionally substituted alkylene (e.g. -CR) ₂ -wherein R is H, alkyl or haloalkyl), optionally substituted haloalkylene or any other linking moiety described herein.

The second structure may comprise a polyimide-based polymer. In some embodiments, the second structure comprises a polymer unit selected from the group consisting of:

and salts thereof, wherein:

L ¹ 、L ² and L ³ Independently a linking moiety;

m is an integer of 1 or more; and

In certain embodiments, at least one of rings a-e is substituted with an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted aromatic group, an optionally substituted aryl group, an ionizable moiety, or an ionic moiety. In some embodiments, at least ring b or c is substituted with an ionizable or ionic moiety. In particular embodiments, the ionic moiety comprises or is-L ^A -X ^A Wherein L is ^A Is a linking moiety (e.g. optionally substituted aliphatic, alkylene, heteroaliphatic or heteroalkylene, e.g. C _1-12 、C _1-6 、C _4-12 Or C _6-12 Form (c); and X ^A Is an acidic moiety, a basic moiety, a multi-ionic moiety, a cationic moiety, or an anionic moiety (e.g., amino, ammonium cation, heterocyclic cation, or others herein).

In other embodiments, the linking moiety (e.g., L ¹ 、L ² Or L ³ ) Is a covalent bond, -O-, -SO ₂ -, -C (O) -, an optionally substituted aliphatic group, an optionally substituted alkylene group (e.g. -CR ₂ -wherein R is H, alkyl or haloalkyl), optionally substituted haloalkylene, optionally substituted alkyleneoxy, optionally substituted heteroaliphatic, optionally substituted heteroalkylene, or any other linking moiety described herein.

The second structure may comprise a polyether. A non-limiting second structure may include the following polymer units:

wherein:

n is an integer of 1 or more; and

ring a may optionally be substituted and/or may optionally include an ionizable or ionic moiety. Non-limiting substituents for ring a include one or more of the aryl groups described herein, e.g., alkyl, alkoxy, alkoxyalkyl, amino, aminoalkyl, aryl, arylalkylene, aroyl, aryloxy, arylalkoxy, cyano, hydroxy, hydroxyalkyl, nitro, halogen, and haloalkyl.

The second structure may be aromatic. A non-limiting second structure may include the following polymer units:

wherein Ar is an optionally substituted arylene or an optionally substituted aromatic group; ak is optionally substituted alkylene, optionally substituted haloalkylene, optionally substituted aliphatic, optionally substituted heteroalkylene, or optionally substituted heteroaliphatic; l is a linking moiety (e.g., any of those described herein); and Ar, L or Ak may be optionally substituted with one or more ionizable or ionic moieties. Non-limiting examples of Ar include, for example, phenylene (e.g., 1, 4-phenylene, 1, 3-phenylene, etc.), biphenylene (e.g., 4 '-biphenylene, 3' -biphenylene, 3,4 '-biphenylene, etc.), terphenylene (e.g., 4' -terphenylene), triphenylene, diphenyl ether, anthracene (e.g., 9, 10-anthracene), naphthalene (e.g., 1, 5-naphthalene, 1, 4-naphthalene, 2, 6-naphthalene, 2, 7-naphthalene, etc.), tetrafluorophenylene (e.g., 1, 4-tetrafluorophenylene, 1, 3-tetrafluorophenylene), etc., as well as others described herein. Non-limiting substituents for Ar include one or more of the aryl groups described herein, e.g., alkyl, alkoxy, alkoxyalkyl, amino, aminoalkyl, aryl, arylalkylene, aroyl, aryloxy, arylalkoxy, cyano, hydroxy, hydroxyalkyl, nitro, halogen, and haloalkyl.

For any of the second structures described herein, each of m, m1, m2, and m3Each independently is an integer of 1 or more. In any of the embodiments herein (e.g., for the second structure), the linking moiety (e.g., L, L) ¹ 、L ² 、L ³ And L ⁴ ) Is or comprises a covalent bond, -O-, -SO ₂ -、-NR ^N1 -, -C (O) -, an optionally substituted aliphatic group, an optionally substituted alkylene group (e.g. -CR ₂ -wherein R is H, alkyl or haloalkyl), optionally substituted haloalkylene, optionally substituted hydroxyalkylene, optionally substituted alkyleneoxy, optionally substituted heteroaliphatic, optionally substituted heteroalkylene, optionally substituted aromatic, optionally substituted arylene, optionally substituted aryleneoxy, optionally substituted heterocycle or optionally substituted heterocyclediyl.

For any of the first or second structures described herein, there may be one or more haloalkyl groups (e.g., attached to the backbone group, aryl group, or another portion of the structure). Non-limiting haloalkyl groups include fluoroalkyl groups (e.g., -C _x F _y H _z ) Perfluoroalkyl (e.g. -C) _x F _y ) Chloroalkyl (e.g. -C) _x Cl _y H _z ) Perchloroalkyl radicals (e.g. -C) _x Cl _y ) Bromoalkyl (e.g. -C) _x Br _y H _z ) Full bromoalkyl (e.g. -C) _x Br _y ) Iodinated alkyl groups (e.g. -C) _x I _y H _z ) Or a periodate group (e.g. -C _x I _y ). In some embodiments, x is 1-6, y is 1-13 and z is 0-12. In a particular embodiment, z=2x+1-y. In other embodiments, x is 1-6, y is 3-13 and z is 0 (e.g., sum y=2x+1).

Additional polymer units

The composition, first structure(s), and second structure(s) herein may include two or more polymeric units that are linked to each other directly or indirectly (e.g., by way of linking moieties). The polymer units may be homopolymers, copolymers, block copolymers, polymer blends, or other useful combinations of repeating monomer units. Additional monomer and polymer units that can be used within the first and/or second structures are provided below.

The monomer units can include optionally substituted aliphatic groups, optionally substituted aromatic groups, and combinations thereof. Non-limiting monomer units can include optionally substituted arylene, optionally substituted aryloxy, optionally substituted alkylene, or combinations thereof, such as optionally substituted (aryl) (alkyl) subunits (e.g., -Ak-Ar-or-Ak-Ar-Ak-or-Ar-Ak-, where Ar is optionally substituted arylene and Ak is optionally substituted alkylene).

Other monomer units may include:

wherein Ar is an optionally substituted arylene or an optionally substituted aromatic group; ak is optionally substituted alkylene or optionally substituted haloalkylene, optionally substituted heteroalkylene, optionally substituted aliphatic or optionally substituted heteroaliphatic; and L is a linking moiety (e.g., any of those described herein) or can be-C (R ⁷ )(R ⁸ ) -. One or more monomer units may be optionally substituted with one or more ionizable or ionic moieties (e.g., as described herein). In certain embodiments, at least one monomeric unit is substituted with one or more ionizable or ionic moieties.

One or more monomer units may be combined to form a polymer unit. Non-limiting polymer units include any of the following:

wherein Ar is an optionally substituted arylene or optionally substituted aromatic group, ak is an optionally substituted alkylene or optionally substituted aliphatic group, L is a linking moiety (e.g., any of those described herein), each n is independently an integer of 1 or greater, and each m is independently 0 or 1 or greaterAn integer. Any number and type of monomer units may be combined to form a polymer unit.

In certain embodiments, the polymer unit comprises more than one arylene group. For example, in a polymer unit having such a structure:

n may be greater than 1 and/or Ar may include two or more aromatic or arylene groups. The presence of such aromatic groups can be used to build a straight chain within the composition.

In other embodiments, L is optionally substituted C _1-6 Aliphatic radical, optionally substituted C _1-6 Alkylene, optionally substituted C _1-6 A heteroalkylene group. The use of short linking groups may provide a denser polymer network because shorter linking groups may minimize self-cyclization reactions.

In some embodiments of the polymer unit, L is a covalent bond, -O-, -NR ^N1 -、-C(O)-、-SO ₂ Optionally substituted alkylene (e.g. -CH ₂ -or-C (CH) ₃ ) ₂ (-), optionally substituted alkyleneoxy, optionally substituted haloalkylene (e.g. -CF ₂ -or-C (CF) ₃ ) ₂ (-), optionally substituted heteroalkylene, optionally substituted arylene, optionally substituted aryleneoxy, optionally substituted heterocyclodiyl, -SO ₂ -NR ^N1 -Ak-、-(O-Ak) _L1 -SO ₂ -NR ^N1 -Ak-、-Ak-、-Ak-(O-Ak) _L1 -、-(O-Ak) _L1 -、-(Ak-O) _L1 -, -C (O) O-Ak-; -Ar-or-Ar-O-, and combinations thereof. In certain embodiments, ak is optionally substituted alkylene or optionally substituted haloalkylene; r is R ^N1 Is H or optionally substituted alkyl or optionally substituted aryl; ar is optionally substituted arylene; and L1 is an integer from 1 to 3.

In one example, the polymer subunits may lack an ionic moiety. Alternatively, the polymer subunits may comprise ionic moieties on the Ar groups, the L groups, both Ar and L groups, or be integrated as part of the L groups. Non-limiting examples of ionizable and ionic moieties include cationic, anionic, and polyionic groups, as described herein.

Further polymer units may comprise poly (benzimidazole) (PBI), polyphenylene (PP), polyimide (PI), poly (ethyleneimine) (PEI), sulfonated Polyimide (SPI), polysulfone (PSF), sulfonated Polysulfone (SPSF), poly (ether ketone) (PEEK), phenolphthalein-PEEK (PEEK-WC), polyethersulfone (PES), sulfonated Polyethersulfone (SPES), sulfonated poly (ether ketone) (SPEEK), phenolphthalein-SPEEK (SPEEK-WC), poly (p-phenylene ether) (PPO), sulfonated polyphenylene oxide (SPPO), ethylene tetrafluoroethylene copolymer (ETFE), polytetrafluoroethylene (PTFE), poly (epichlorohydrin) (PECH), poly (styrene) (PS), sulfonated poly (styrene) (SPS), hydrogenated poly (butadiene-styrene) (HPBS), styrene divinylbenzene copolymer (SDVB), styrene-ethylene-butylene-styrene copolymer (SEBS), sulfonated bisphenol-A-polysulfone (SU), poly (4-phenoxybenzoyl-1, 4-phenylene) (SPBP), sulfonated poly (4-phenoxybenzoyl-1, 4-phenylene) (PPP), poly (phosphonitrile) (PPPVA), poly (phosphonitrile) (PPP), polyetherimides, and combinations thereof.

Crosslinking agent

In addition, crosslinking within the material may be facilitated through the use of crosslinking agents. For example, the composition may include polymer units and the crosslinking agent may be used to provide crosslinking between the polymer units. For example, if the polymeric units (P1 and P2) include leaving groups, then the diamine crosslinking reagent (e.g., H ₂ N-Ak-NH ₂ ) Can be used for polymer singleThe meta-reaction is carried out by displacing the leaving group and forming an amino-containing cross-linked structure within the composition (e.g. thereby forming P1-NH-Ak-NH-P2). Such cross-linked structures may be formed between combinations of the first and second structures (e.g., between two first structures, between two second structures, between first and second structures, etc.). The crosslinked structure may be introduced as follows: the crosslinked structure is formed by forming a polymer composition and then exposing the composition to a crosslinking agent.

In some cases, the crosslinking agent is a multivalent amine, such as diamine, triamine, tetramine, pentamine, and the like. Non-limiting amine-containing crosslinking reagents may include:

wherein Ak is an optionally substituted aliphatic or optionally substituted alkylene, ar is an optionally substituted aromatic or optionally substituted arylene, L is a linking moiety (e.g., any of the moieties herein, e.g., covalent bonds, optionally substituted alkylene, optionally substituted aliphatic, etc.), L3 is an integer of 2 or greater (e.g., 2, 3, 4, 5, 6, or greater), and R ^N1 And R is ^N2 Independently is H or optionally substituted alkyl. Still another example of an amine-containing linking agent includes 1, 6-diaminohexane (hexamethylenediamine), 1, 4-diaminobutane, 1, 8-diaminooctane, propane-1, 2, 3-triamine, [1,1':3', 1' -terphenyl]-4,4",5' -triamine and others.

Depending on the functional groups present in the material, the crosslinking reagent may include nucleophilic groups (e.g., amine or hydroxyl groups) or electrophilic groups (e.g., carbonyl groups). Thus, non-limiting crosslinking reagents may include amine-containing reagents, hydroxyl-containing reagents, carboxylic acid-containing reagents, acid halide-containing reagents, and the like. In addition, the crosslinking reagent may include:

wherein Ak is an optionally substituted aliphatic or optionally substituted alkylene, ar is an optionally substituted aromatic or optionally substituted arylene, L is a linking moiety (e.g., any of the herein,such as covalent bonds, optionally substituted alkylene groups, optionally substituted aliphatic groups, etc.), L3 is an integer of 2 or greater (e.g., 2,3, 4, 5, 6, or greater), and X is halo, hydroxy, optionally substituted amino, hydroxy, carboxy, acyl halide (e.g., -C (O) -R, where R is halo), formaldehyde (e.g., -C (O) H), or optionally substituted alkyl. Non-limiting crosslinking agents may include terephthalaldehyde, glutaraldehyde, ortho-xylene, para-xylene, or meta-xylene.

After reacting the crosslinking reagent, the composition may include one or more crosslinking structures within the composition. If the crosslinking reagent is divalent, the crosslinking structure may be present between the two of the first structure(s), the second structure(s), any combination of the polymeric monomer and the ionizable/ionic moiety (e.g., between two polymeric units, between two ionizable/ionic moieties, etc.). If the crosslinking reagent is trivalent or has a higher n-valence state, the crosslinking structure may exist between any n of the polymer units, the linking moieties, the ionizable moieties, and/or the ionic moieties. Non-limiting cross-linking structures present in the composition include those cross-linking structures that are formed after reacting the cross-linking agent. Thus, examples of cross-linked structures may include:

wherein Ak is an optionally substituted aliphatic or optionally substituted alkylene, ar is an optionally substituted aromatic or optionally substituted arylene, L is a linking moiety (e.g., any of the herein, e.g., covalent bonds, optionally substituted alkylene, optionally substituted aliphatic, etc.), L3 is an integer of 2 or greater (e.g., 2, 3, 4, 5, 6, or greater), and X' is a form after X is reacted. In some embodiments, X' is absent, -O-, -NR ^N1 -, -C (O) -or-Ak-wherein R ^N1 Is H or optionally substituted alkyl, and Ak is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted aliphatic or optionally substituted heteroaliphatic.

Ionizable and ionic moieties

The compositions herein may include one or more ionizable or ionic moieties. Such moieties may include anionic or cationic charges, for example in ionic moieties. Alternatively, the ionizable moiety comprises a functional group that can be readily converted to an ionic moiety, e.g., can be readily deprotonated to form a carboxylate anion (-CO) ₂ ^- ) Carboxyl group (-CO) ₂ H) Is described herein, is an ionizable moiety. As used herein, the terms "ionizable" and "ionic" are used interchangeably.

The ionizable or ionic moieties may be provided in the composition in any useful manner. In one embodiment, at least one of the first and second structures independently comprises one or more ionizable/ionic moieties. In another embodiment, both the first and second structures independently comprise one or more ionizable/ionic moieties.

The moiety may be characterized as an acidic moiety (e.g., a moiety that may be deprotonated or may carry a negative charge) or a basic moiety (e.g., a moiety that may be protonated or may carry a positive charge). In particular embodiments, the moiety may be a multi-ionic moiety, which may include multiple acidic moieties, multiple basic moieties, or a combination thereof (e.g., in a zwitterionic moiety). In addition, the moieties may include zwitterionic moieties such as those comprising anionic moieties (e.g., hydroxyl or deprotonated hydroxyl) and cationic moieties (e.g., ammonium).

The ionic moieties herein may be linked to the parent structure through one or more linking moieties. Further, a single ion moiety may extend from a single connecting moiety, or multiple ion moieties may have one or more connecting moieties therebetween.

For example, the ionic moiety may have any of the following structures: -L ^A -X ^A or-L ^A -(L ^A’ -X ^A ) _L2 or-L ^A -(X ^A -L ^A’ -X ^A’ ) _L2 or-L ^A -X ^A -L ^A’ -X ^A’ -L ^A” -X ^A” Wherein each L ^A 、L ^A’ And L ^A” Is a connecting structure part; each X is ^A 、X ^A’ And X ^A” Independently comprising an acidic moiety, a basic moiety, or a polyionic moiety; and L2 is an integer of 1, 2, 3 or more (e.g., 1-20).

Non-limiting linking moieties (e.g. for L ^A 、L ^A’ And L ^A” For the sake of simplicity) comprises covalent bonds, spiro bonds, -O-, -NR ^N1 -、-SO ₂ -NR ^N1 -Ak-、-(O-Ak) _L1 -SO ₂ -NR ^N1 -Ak-、-Ak-、-Ak-(O-Ak) _L1 -、-(O-Ak) _L1 -、-(Ak-O) _L1 -, -C (O) O-Ak-; -Ar-or-Ar-O-, wherein Ak is optionally substituted alkylene or optionally substituted haloalkylene, R ^N1 Is H or optionally substituted alkyl, ar is optionally substituted arylene, and L1 is an integer from 1 to 3. In particular embodiments, L ^A Is- (CH) ₂ ) _L1 -、-O(CH ₂ ) _L1 -、-(CF ₂ ) _L1 -、-O(CF ₂ ) _L1 -or-S (CF) ₂ ) _L1 -, wherein L1 is an integer from 1 to 3.

In some cases, the linker is linked to the structural distribution of two or more ions. In some embodiments, the ionic moiety may be-L ^A -(L ^A’ -X ^A ) _L2 Wherein L is ^A And L ^A’ Is a linking moiety and X ^A Is an acidic moiety, a basic moiety or a polycyclic moiety. In one case, L ^A One, two or three linkers are provided. Non-limiting L ^A Can be-CX ₂ (CX ₂ -)、-CX(CX ₂ -) ₂ or-C (CX) ₂ -) ₃ Wherein X is H, alkyl or halo. L (L) ^A’ A connection point to the ion structure portion may then be provided. For example, L ^A1’ Can be- (CH) ₂ ) _L1 -、-O(CH ₂ ) _L1 -、-(CF ₂ ) _L1 -、-O(CF ₂ ) _L1 -or-S (CF) ₂ ) _L1 -, wherein L1 is an integer from 1 to 3; and X ^A Is any ionizable or ionic moiety described herein.

Non-limiting ionic moieties include carboxyl groups (-CO) ₂ H) Carboxylate anions (-CO) ₂ ^- ) GuanidineCations (e.g. -NR) ^N1 -C(＝NR ^N2 R ^N3 )(NR ^N4 R ^N5 ) Or (b)>N＝C(NR ^N2 R ^N3 )(NR ^N4 R ^N5 ) Or a salt form thereof. R is R ^N1 、R ^N2 、R ^N3 、R ^N4 And R is ^N5 Non-limiting examples of each of (a) are independently H, optionally substituted alkyl, optionally substituted aryl, or optionally substituted amino; or R is ^N1 And R is ^N2 、R ^N2 And R is ^N3 、R ^N3 And R is ^N4 、R ^N1 And R is ^N2 Or R is ^N1 And R is ^N4 Forms together with the nitrogen atom to which each is attached an optionally substituted heterocyclyl, heterocycle, or heterocyclic cation, as defined herein.

Some ion moieties may include one or more sulfur atoms. Non-limiting sulfur-containing moieties include sulfonic acid groups (-SO) ₂ OH), sulfonate anions (-SO) ₂ O ^- ) Sulfonium cations (e.g. -SR ^S1 R ^S2 ) Sulfate ester group (e.g. -O-S (=O) ₂ (OR ^S1 ) Sulfate anion (-O-S (=o) ₂ O-) or a salt form thereof. R is R ^S1 And R is ^S2 Non-limiting examples of each of (a) are independently H, optionally substituted alkyl, optionally substituted aryl, or optionally substituted amino; or R is ^S1 And R is ^S2 Forms an optionally substituted heterocyclyl, heterocycle, or heterocyclic cation, together with the sulfur atom to which each is attached, as defined herein; or R is ^S1 And R is ^S2 Together forming an optionally substituted alkylene or heteroalkylene (e.g., as described herein).

Other ionic moieties may include one or more phosphorus atoms. Non-limiting phosphorus-containing moieties include phosphonic acid groups (e.g., -P (=o) (OH) ₂ ) Phosphonate anions (e.g. -P (=o) (O) ^- ) ₂ or-P (=O) (OH) (O ^- ) Phosphate groups (e.g. -O-P (=o) (OR) ^P1 )(OR ^P2 ) OR-O- [ P (=O) (OR) ^P1 )-O] _P3 -R ^P2 ) Phosphate anions (e.g. -O-P (=o) (OR) ^P1 )(O ^- ) or-O-P (=O) (O) ^- ) ₂ )、Cations (e.g. -P) ⁺ R ^P1 R ^P2 R ^P3 ) Phosphazene->Cations (e.g. -P) ⁺ (＝NR ^N1 R ^N2 )R ^P1 R ^P2 Wherein R is ^N1 And R is ^N2 Independently an optionally substituted alkyl or optionally substituted aryl), or salt forms thereof. R is R ^P1 、R ^P2 And R is ^P3 Non-limiting examples of each of (a) are independently H, optionally substituted alkyl, optionally substituted aryl, or optionally substituted amino; or R is ^P1 And R is ^P2 Forms together with the phosphorus atom to which each is attached an optionally substituted heterocyclyl, heterocycle, or heterocyclic cation, as defined herein; or R is ^P1 And R is ^P2 And R is ^P3 Forms together with the phosphorus atom to which each is attached an optionally substituted heterocyclyl, heterocycle, or heterocyclic cation, as defined herein; or a single, two or delocalized pi bond, provided that the combination of bonds results in tetravalent phosphorus; or wherein R is ^P1 、R ^P2 And R is ^P3 Together form an optionally substituted alkylene or heteroalkylene (e.g., as described herein).

Other ionic moieties may include one or more nitrogen atoms. Non-limiting nitrogen-containing moieties include amino groups (e.g., -NR ^N1 R ^N2 ) Ammonium cations (e.g. -N) ⁺ R ^N1 R ^N2 R ^N3 or-N ⁺ R ^N1 R ^N2 (-), heterocyclic cations (e.g. piperidine, 1-dialkyl-piperidine) Pyrrolidine->1, 1-dialkyl-pyrrolidine +.>Pyridine->1-alkylpyridine->(1, 4-diazabicyclo [ 2.2.2)]Octanoyl-1-yl) (DABCO), 4-alkyl- (1, 4-diazabicyclo [2.2.2 ]]Octanoyl-1-yl), etc.), or salt forms thereof. R is R ^N1 、R ^N2 And R is ^N3 Non-limiting examples of each of (a) are independently H, optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted aryl; or R is ^N1 And R is ^N2 Forms together with the nitrogen atom to which each is attached an optionally substituted heterocyclyl, heterocycle, or heterocyclic cation, as defined herein; or R is ^N1 And R is ^N2 And R is ^N3 Forms together with the nitrogen atom to which each is attached an optionally substituted heterocyclyl, heterocycle, or heterocyclic cation, as defined herein; or wherein R is ^N1 、R ^N2 And R is ^N3 Together form an optionally substituted alkylene or heteroalkylene (e.g., as described herein); or a single, two or delocalized pi bond, provided that the combination of bonds results in a tetravalent nitrogen.

Other heterocyclic cations include piperidineCations, e.g. dimethylpiperidine +.>Methylpiperidine->(e.g. 1-methyl-piperidine->-1-yl), ethylmethylpiperidine->Ethylpiperidine->(e.g. 1-ethyl-piperidine->-1-yl), propylmethylpiperidine->Propylpiperidine->(e.g. 1-propyl-piperidine->-1-yl), butylmethylpiperidine->Butyl piperidine- >(e.g. 1-butyl-piperidine->-1-yl), diethylpiperidine->Propylethylpiperidine->Butyl Ethylpiperidine->Butyl propyl piperidine->Or spiro-1, 1' -bipiperidine +.>Pyrrolidine->Cations, e.g. dimethylpyrrolidine +.>Ethylmethylpyrrolidine->Propyl methyl pyrrolidone->Butyl methyl pyrrolidine->Diethyl pyrrolidine->Propylethylpyrrolidine->Butyl ethyl pyrrolidine->Butyl propyl pyrrolidine->Spiro-1, 1' -bipyrrolidine +.>Spiro-1-pyrrolidine->-1' -piperidineOr spiro-1-pyrrolidine->-1' -morpholino->Pyrazole->Cations, e.g. dimethylpyrazole +.>Ethylmethylpyrazole->Or butylmethylpyrazole->Imidazole->Cations, e.g. 3-alkylimidazole +.>1, 2-dialkylimidazole->For example 1, 2-dimethyl-1H-imidazole-3->Those cations having one nitrogen and five or six carbon ring members, e.g. pyridine +.>2-methylpyridine->3-methylpyridine->4-methylpyridine->2, 6-lutidine->Quinoline->Isoquinoline->Acridine->Or phenanthridine->Those cations having two nitrogen and four carbocycle members, e.g. pyridazin +.>Pyrimidine->Pyrazine->Or phenazine->Or those having one nitrogen and one oxygen ring member, e.g. morpholino->2-methylmorpholine->Or 3-methylmorpholine->

Any of the heterocyclic cations may be linked to the polymer either directly or indirectly (e.g., via a linker or linking moiety). Furthermore, any atom within the heterocyclic cation (e.g., within the ring of the heterocyclic cation) may be attached to the polymer. For example, with piperidines As non-limiting heterocyclic cations, such cations may be attached to the polymer through a cationic center or through an atom within the ring, and such attachment may be direct through a covalent bond or through L ^A (a linking moiety, such as any of those described herein) is indirect:

(piperidine-1-)>-1-yl), -a method of preparing a polypeptide>(by L ^A Linked piperidine-1->-1-yl),

(piperidine-1-)>-4-yl) or->(by L ^A Linked piperidine-1->-4-yl). Except for piperidine-1->In addition to the 1-or 4-position connection of (2), other connection positions may be implemented at any point on the ring.

In some embodiments, the heterocyclic cation is or comprises piperidineCationic or azepane->And (3) cations. In one embodiment, the heterocyclic cation comprises the following structure:

wherein:

R ^N1 is H, an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted heteroaliphatic group, an optionally substituted heteroalkyl group, an optionally substituted aromatic group, or an optionally substituted aryl group;

n is 1, 2, 3, 4 or 5; and

each R ^a Independently H, an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted heteroaliphatic group, an optionally substituted heteroalkyl group, an optionally substituted aromatic group, an optionally substituted aryl group, an ionizable moiety, or an ionic moiety;

Wherein R is ^N1 And at least one R ^a May together form an optionally substituted cyclic group or an optionally substituted heterocyclic group, and/or

Wherein at least two R ^a The groups may together form an optionally substituted cyclic group or an optionally substituted heterocyclic group.

In one case, R ^N1 And R is ^a May together form an optionally substituted alkylene group or an optionally substituted heteroalkylene group. In certain embodiments, the alkylene or heteroalkylene groups are independently substituted with one or more ionizable or ionic moieties (e.g., any of those described herein).

In another case, at least one R ^a Is an optionally substituted aliphatic group or an optionally substituted alkyl group. R is R ^a Non-limiting examples of (a) include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, tert-pentyl, neopentyl, 3-pentyl, sec-isopentyl, and the like. In other embodiments, the heterocyclic cation has a ring with one, two, three, four, five, or six R's other than H ^a A group. In other embodiments, the heterocyclic cation has a ring with one, two, three, four, five, or six R' s ^a A group, R ^a The groups are independently optionally substituted aliphatic groups or optionally substituted alkyl groups. Without wishing to be limited by a mechanism, the presence of bulky substituents may provide a more stable cation. In other embodiments, any of the ionizable or ionic moieties herein may be substituted with one or more R ^a And (3) group substitution.

Other non-limiting piperidinesCationic or azepane->The cations include any of the following:

etc.

Other structural parts may include-L ^A -L ^A’ -X ^A Wherein L is ^A Is or includes an optionally substituted aromatic group, an optionally substituted arylene group, an optionally substituted heterocycle, or an optionally substituted heterocyclyl group (e.g., an optionally substituted phenylene group or an optionally substituted arylene group); l (L) ^A’ Is or includes an optionally substituted aliphatic group, an optionally substituted alkylene group, an optionally substituted heteroaliphatic group or an optionally substituted heteroalkylene group (e.g., optionally substituted C _1-6 Alkylene or optionally substituted C _1-6 A heteroalkylene group); and X ^A Is or includes an ionic moiety comprising one or more nitrogen atoms. Non-limiting ionic moieties include pyridine(e.g. pyridine->-1-yl (pyridinum-1-yl, pyrd); alkylpyridine->For example 2-methylpyridine- >-1-yl (2 mpyd); or aromatic pyridine->For example 1-benzyl pyridine->-4-yl), imidazole->(e.g. 1, 2-dialkylimidazole +.>-3-yl, including 1, 2-dimethylimidazole +.>-3-yl (1, 2-DMim)), 4-aza-1-nitrogen +.>Bicyclo [2.2.2]Oct-1-yl (or 1, 4-diazabicyclo [ 2.2.2)]Octane (DABCO) cation), 4-alkyl-1, 4-diaza +.>Bicyclo [2.2.2]Oct-1-yl (e.g. 4-methyl-1, 4-diaza +.>Bicyclo [2.2.2]Oct-1-yl (MAABCO) cation), 4-benzyl-1, 4-diaza->Bicyclo [2.2.2]Oct-1-yl (or 1-benzyl-1, 4-diaza +.>Bicyclo [2.2.2]Octane (BABCO) cation), aliphatic ammonium (e.g., hexyldimethyl-ammonium-1-yl (DMHA), dicyclohexylmethyl-ammonium-1-yl (MCH), methyldi-n-propyl-ammonium-1-yl (MnPr), trimethylammonium-1-yl (TMA) or triethylammonium-1-yl (TEA)), aromatic ammonium (e.g., dialkylbenzyl ammonium, such as benzyldimethyl-ammonium-1-yl, benzyldiethyl-ammonium-1-yl, benzylhexyl-methyl-ammonium-1-yl, benzyldi-n-propyl-ammonium-1-yl, benzylmethyl-n-propyl-ammonium-1-yl, benzyldicyclohexylammonium-1-yl, benzylcyclohexylmethyl-ammonium-1-yl, (3-nitrobenzyl) dimethyl-ammonium-1-yl or (3-methoxybenzyl) dimethyl-ammonium-1-yl; or dialkyl (phenylalkyl) ammonium, such as dimethyl (phenylhexyl) ammonium-1-yl and piperidine +. >(e.g. aliphatic piperidines>For example 1-methyl-piperidine->-1-yl (Mepip), 1, 2-dialkyl-piperidine +.>Or 1, 2-dimethyl-piperidine->-4-yl (DMP); or aromatic piperidine->For example 1-benzyl-1-methyl-piperidine-4-yl (BMP), any piperidine +.>A cation).

Other structural parts may include-L ^A -X ^A Wherein L is ^A Is a covalent bond (including a spiro bond), an optionally substituted aliphatic group, an optionally substituted alkylene group, an optionally substituted heteroaliphatic group, an optionally substituted heteroalkylene group, an optionally substituted aromatic group, an optionally substituted arylene group, an optionally substituted heterocycle, or an optionally substituted heterocyclyl group (e.g., optionally substituted C _1-6 Alkylene, optionally substituted C _1-6 Heteroalkylene, optionally substituted phenylene, or optionally substituted aryloxy); and X ^A Is or includes an ionic moiety comprising one or more nitrogen atoms. Non-limiting ionic moieties include pyridine(e.g. pyridine->-1-yl (Pyrd); alkylpyridine->For example 2-methylpyridine->-1-yl (2 mpyd); or aromatic pyridinesFor example 1-benzyl pyridine->-4-yl), imidazole->(e.g. 1, 2-dialkylimidazole +.>-3-yl, including 1, 2-dimethylimidazole +.>-3-yl (1, 2-DMim)), 4-aza-1-nitrogen +. >Bicyclo [2.2.2]Oct-1-yl (or 1, 4-diazabicyclo [ 2.2.2)]Octane (DABCO) cation), 4-alkyl-1, 4-diaza +.>Bicyclo [2.2.2]Oct-1-yl (e.g. 4-methyl-1, 4-diaza +.>Bicyclo [2.2.2]Oct-1-yl (MAABCO) cation), 4-benzyl-1, 4-diaza->Bicyclo [2.2.2]Oct-1-yl (or 1-benzyl-1, 4-diaza +.>Bicyclo [2.2.2]Octane (BABCO) cation), aliphatic ammonium (e.g., hexyldimethyl ammonium-1-yl (DMHA), dicyclohexylmethyl ammonium-1-ylMCH), methyl di-n-propylammonium-1-yl (MnPr), trimethylammonium-1-yl (TMA) or triethylammonium-1-yl (TEA)), aromatic ammonium (e.g. dialkylbenzylammonium, such as benzyldimethylammonium-1-yl, benzyldiethylammonium-1-yl, benzylhexylmethylammonium-1-yl, benzyldi-n-propylammonium-1-yl, benzylmethyl-n-propylammonium-1-yl, benzyldicyclohexylammonium-1-yl, benzylcyclohexylmethylammonium-1-yl, (3-nitrobenzyl) dimethylammonium-1-yl or (3-methoxybenzyl) dimethylammonium-1-yl; or dialkyl (phenylalkyl) ammonium, such as dimethyl (phenylhexyl) ammonium-1-yl and piperidine +.>(e.g. aliphatic piperidines>For example 1-methyl-piperidine->-1-yl, 1, 2-dialkyl-piperidine->Or 1, 2-dimethyl-piperidine->-4-yl (DMP); or aromatic piperidine->For example 1-benzyl-1-methyl-piperidine- >-4-yl (BMP) and any piperidine described hereinA cation).

Such moieties may be associated with one or more counterions. For example, a cationic moiety may be associated with one or more anionic counterions, and an anionic moiety may be associated with one or more cationic counterions.

Arylene group

Specific moieties herein (e.g., polymer units, linking moieties, etc.) may include optionally substituted arylene groups. Such arylene groups include any multivalent (e.g., divalent, trivalent, tetravalent, etc.) groups having one or more aromatic groups, which may include heteroaromatic groups. Non-limiting aromatic groups may include any of the following:

wherein each of rings a-i may be optionally substituted (e.g., with any optional substituent described herein with respect to alkyl or aryl; or any ionic moiety described herein); l' is a linking moiety (e.g., any of those described herein); and each of R' and R "is independently H, optionally substituted alkyl, optionally substituted aryl, or an ionic moiety, as described herein. Non-limiting substituents for rings a-i include one or more substituents described herein with respect to aryl groups, such as alkyl, alkoxy, alkoxyalkyl, amino, aminoalkyl, aryl, arylalkylene, aroyl, aryloxy, arylalkoxy, cyano, hydroxy, hydroxyalkyl, nitro, halo, and haloalkyl. In some embodiments, L' is a covalent bond, -O-, -NR ^N1 -, -C (O) -, optionally substituted alkylene, optionally substituted heteroalkylene, or optionally substituted arylene.

Other non-limiting arylene groups may include phenylene (e.g., 1, 4-phenylene, 1, 3-phenylene, etc.), biphenylene (e.g., 4 '-biphenylene, 3' -biphenylene, 3,4 '-biphenylene, etc.), terphenylene (e.g., 4' -terphenylene), 9, 10-anthracene, naphthalene (e.g., 1, 5-naphthalene, 1, 4-naphthalene, 2, 6-naphthalene, 2, 7-naphthalene, etc.), tetrafluorophenylene (e.g., 1, 4-tetrafluorophenylene, 1, 3-tetrafluorophenylene), etc.

Non-limiting examples of the linking moiety of an arylene group include any of the herein. In some embodiments, L' is substituted with one or more ionizable or ionic moieties described herein. In certain embodiments, L' is optionally substituted alkylene. Non-limiting substituents of L' may include-L ^A -X ^A Wherein L is ^A Is a linking moiety (e.g., any of those described herein, e.g., -Ak-, -O-Ak-, -Ak-O-, -Ar-, -O-Ar-, or-Ar-O-, wherein Ak is optionally substituted alkylene and Ar is optionally substituted arylene), and X ^A Is an acidic moiety, a basic moiety, or a polyionic moiety.

Connecting structural part

Specific chemical functional groups herein may include a linking moiety, between a parent structure and another moiety (e.g., an ionic moiety), or between two (or more) other moieties. Connecting structural parts (e.g. L, L ¹ 、L ² 、L ³ 、L ⁴ 、L ^A 、L ^A’ 、L ^A” 、L ^B’ 、L ^B” 、L ^8A And others) may be any useful multivalent group, for example, an optionally substituted aliphatic group, an optionally substituted heteroaliphatic group, an optionally substituted aromatic group, or an optionally substituted heteroaromatic group in multivalent form.

Non-limiting linking moieties (e.g., L) include covalent bonds, spiro bonds, -O-, -NR ^N1 -、-C(O)-、-C(O)O-、-OC(O)-、-SO ₂ -, optionally substituted alkylene, optionally substituted alkyleneoxy, optionally substituted haloalkylene, optionally substituted heteroalkylene, optionally substituted arylene, optionally substituted aryleneoxy, optionally substituted heterocyclodiyl, -SO ₂ -NR ^N1 -Ak-、-(O-Ak) _L1 -SO ₂ -NR ^N1 -Ak-、-Ak-、-Ak-(O-Ak) _L1 -、-(O-Ak) _L1 -、-(Ak-O) _L1 -, -C (O) O-Ak-; -Ar-or-Ar-O-, and combinations thereof. In certain embodiments, ak is an optionally substituted aliphatic group, an optionally substituted alkylene group, or an optionally substituted haloalkylene group;R ^N1 is H or optionally substituted alkyl or optionally substituted aryl; ar is an optionally substituted aromatic group or an optionally substituted arylene group; and L1 is an integer from 1 to 3.

In some embodiments, the linking moiety is- (CH) ₂ ) _L1 -、-O(CH ₂ ) _L1 -、-(CF ₂ ) _L1 -、-O(CF ₂ ) _L1 -or-S (CF) ₂ ) _L1 -, wherein L1 is an integer from 1 to 3. In other embodiments, the linking moiety is-Ak-O-Ar-Ak-O-Ak-or-Ak-O-Ar-, wherein Ak is optionally substituted alkylene or optionally substituted haloalkylene, and Ar is optionally substituted arylene. Non-limiting substitutions of Ar include-SO ₂ -Ph, wherein Ph may be unsubstituted or substituted with one or more halogens.

Process for preparing polymers

The present disclosure also encompasses methods of preparing the polymers. One non-limiting method can include forming an initial polymer having a reactive group (e.g., a halo group or another leaving group) and replacing the reactive group with an ionic moiety, thereby providing an ionic polymer. Any useful synthetic scheme may be used to provide such ionizable or ionic moieties, such as by sulfonation or oxidation to introduce such ionizable/ionic moieties, catalytic polymerization of monomers having such ionizable/ionic moieties, and the like.

Additional steps may include exchanging the counter-ion present in the ionic polymer with another counter-ion (e.g., exchanging the hydroxyl counter-ion with a halide counter-ion). Further steps may include exposing the ionomer to a crosslinking agent to form one or more crosslinked structures between polymer units, ionizable moieties, or combinations of ionic moieties.

The initial polymer may be a copolymer or homopolymer formed in any useful manner. In one embodiment, the method includes providing one or more polymer units (or monomer units), thereby forming a polymer. In particular embodiments, friedel-crafts alkylating agents are used to react between monomer units (e.g., the same or different monomer units). For example, friedel-crafts alkylating agents can provide carbocation intermediates having an electron withdrawing moiety and a reactive group, wherein the carbocation center reacts with the aryl group of the monomer unit. The resulting initial polymer may then include an electron withdrawing moiety (e.g., R in formula (I) ⁷ ) And a reactive group attached to the polymer.

Scheme 1

Scheme 1 provides a non-limiting reaction scheme for preparing polymers. The reaction can be carried out by providing a first structuring agent (1) and a second structuring agent (2), each having an optionally substituted arylene (-Ar 1-or-Ar 2-) and a leaving group (LG, e.g., H). Also provided are non-limiting Friedel-crafts alkylating agents (3) in the optional presence of strong acids (e.g. methane sulphonic acid) which can be used to react between monomer units (provided by 1 and 2). For example, friedel-crafts alkylating agents can be provided having haloalkyl or other electron-withdrawing moieties (e.g., R ⁷ ) And a moiety linked to the carbonyl carbon through a linking moiety (L ^A ) Carbocationic intermediates of linked reactive groups (RG, e.g., halo). After electrophilic addition reaction, the resulting initial polymer (4) comprises electron withdrawing moieties (e.g., R ⁷ ) And through the connecting structural part L ^A Reactive Groups (RG) attached to carbons in the vicinity of the arylene groups (-Ar 1-and-Ar 2-).

Additional reactions may include substitution of the reactive group RG with an example ionizable reagent (5), thereby providing a compound having an ionic moiety (-X) ^A+ ) An ionomer (6). A further step may comprise the use of a further counterion (A ^- ) (7) counter ion (RG) present in ion exchange polymer (6) ^- ) Thereby providing an additional ionomer (8). As can be seen, the ionomer (8) comprises a non-limiting first structure (S1) and a non-limiting second structure (S2).

Other steps may include exposing the initial polymer (4) or ionic polymer (6, 8) to a crosslinking agent to form one or more crosslinked structures between polymer units, ionizable moieties, or combinations of ionic moieties.

Scheme 2

Scheme 2 provides another non-limiting reaction scheme for preparing polymers. The reaction may be carried out by providing a first structuring agent (9) having an optionally substituted arylene (-Ar 1-) and a leaving group (LG, e.g., H) with a second structuring agent (10) having a carbonyl carbon and an S2' moiety (e.g., a heterocyclic or cycloaliphatic group). Also provided are non-limiting Friedel-crafts alkylating agents (3) in the optional presence of strong acids (e.g. methane sulphonic acid) which can be used to react between monomer units (provided by 9). For example, friedel-crafts alkylating agents can be provided having electron withdrawing moieties (e.g., R ⁷ ) And a moiety linked to the carbonyl carbon through a linking moiety (L ^A ) Carbocationic intermediates of linked reactive groups (RG, e.g., halo). Here, the carbonyl carbons in (10) and (3) can both provide electrophilically added carbocation reactive intermediates to the aryl group Ar1 provided by reagent (9). After the electrophilic addition reaction, the resulting initial polymer (11) comprises electron withdrawing moieties (e.g., R ⁷ ) And through the connecting structural part L ^A A Reactive Group (RG) attached to a carbon near the arylene group (-Ar 1-), and an S2' moiety near the arylene group (-Ar 1-). In this way, the copolymer may include the same arylene moiety (-Ar-) in the first and second structures.

Additional reactions may include substitution of the reactive group RG with an example ionizable reagent (5), thereby providing a compound having an ionic moiety (-X) ^A+ ) Is an ionic polymer (12). A further step may comprise the use of a further counterion (A ^- ) (7) counter ion (RG) present in ion-exchanged polymer (12) ^- ) Thereby providing an additional ionomer (13). As can be seen, the ionomer (13) comprises a non-limiting first structure (S1) and a non-limiting second structure (S2). Other steps may include exposing the initial polymer (11) or the ionic polymer (12, 13) to a crosslinking agent from While one or more cross-linked structures are formed between the polymer units, the ionizable moieties, or a combination of ionic moieties.

Scheme 3

Alternatively, the copolymer may be first formed and then functionalized to provide ionizable or ionic moieties. Scheme 3 provides a non-limiting reaction scheme for preparing polymers. By providing an electron withdrawing moiety (e.g., R) having an optionally substituted arylene (-Ar 1-or-Ar 2-) ⁷ ) And a moiety (L) bonded to carbon through a bond ^A ) The initial polymer (14) of attached reactive groups (RG, e.g., halo groups) is reacted. Also provided are the use of a catalyst (e.g., a Lewis acid, e.g., znCl) in the presence of a halogen acid (e.g., HZ (16), e.g., HCl, HBr, HI or HF) ₂ Or AlCl ₃ ) In the case of (c) an alkylating agent (e.g., formaldehyde 15) which can be used to react with the aryl groups Ar1 and Ar2 (provided by 14). Here, the carbonyl carbons in (15) may both provide electrophilically added carbocation reactive intermediates to aryl groups Ar1 and Ar 2. After electrophilic addition reaction and halide (Z) addition, the resulting initial polymer (17) comprises halomethyl (-CH) ₂ X) a group or an aryl group.

Additional reactions may include substitution of the halo group Z and the reactive group RG with example ionizable reagent (5), thereby providing a compound having an ionic moiety (-X) ^A+ ) Is an ionic polymer (18). A further step may comprise the use of a further counterion (A ^- ) (7) counter ion (RG) present in ion exchange polymer (18) ^- ) Thereby providing an additional ionomer (19). As can be seen, the ionomer (19) comprises a non-limiting first structure (S1) and a non-limiting second structure (S2). Other steps may include exposing the initial polymer (14, 17) or ionic polymer (18, 19) to a crosslinking agent to form one or more crosslinked structures between polymer units, ionizable moieties, or combinations of ionic moieties.

Scheme 4

Scheme 4 provides another non-limiting reaction scheme for preparing polymers. By providing an electron withdrawing moiety (e.g., R) having an optionally substituted arylene (-Ar 1-or-Ar 2-) ⁷ ) And a moiety (L) bonded to carbon through a bond ^A ) The initial polymer (14) of attached reactive groups (RG, e.g., halo groups) is reacted. Also provided are non-limiting Friedel-crafts alkylating agents (20) which are useful in reacting with aryl groups Ar1 and Ar2 (provided by 14) optionally in the presence of a strong acid such as methane sulfonic acid. For example, friedel-crafts alkylating agents can be provided having a leaving group (LG, e.g. hydroxy) and having a moiety (L ^A ) Carbocationic intermediates of reactive groups (RG, e.g., halo) linked together. After the electrophilic addition reaction, the resulting initial polymer (21) comprises a moiety L on the aryl groups Ar1 and Ar2 via a linkage ^A An attached RG (e.g., halo).

Additional reactions may include substitution of the reactive group RG with an example ionizable reagent (5), thereby providing a compound having an ionic moiety (-X) ^A+ ) Is an ionomer (22). A further step may comprise the use of a further counterion (A ^- ) (7) counter ion (RG) present in ion exchange polymer (22) ^- ) Thereby providing an additional ionomer (23). As can be seen, the ionomer (23) comprises a non-limiting first structure (S1) and a non-limiting second structure (S2). Other steps may include exposing the initial polymer (14, 21) or ionic polymer (22, 23) to a crosslinking agent to form one or more crosslinked structures between polymer units, ionizable moieties, or combinations of ionic moieties.

Use of the same

The compositions herein can be used to form materials such as films, membranes (e.g., ion exchange membranes) or crosslinked polymer matrices. Their compositions and materials can be used in devices or instruments such as electrochemical cells. In one embodiment, an electrochemical cell includes an anode, a cathode, and a Polymer Electrolyte Membrane (PEM) disposed between the anode and the cathode. The PEM (or component thereof) may comprise any of the compositions or materials described herein.

The compositions herein are useful as components of Membrane Electrode Assemblies (MEA). The non-limiting MEA may include a cathode layer having a reduction catalyst and a first ion-conducting polymer; an anode layer having an oxidation catalyst and a second ion-conducting polymer; a membrane layer having a third ion-conducting polymer between the anode layer and the cathode layer; and a cathode buffer layer having a fourth ion conducting polymer between the cathode layer and the membrane layer. A membrane layer (e.g., PEM) may provide ionic communication between or may conductively connect the cathode layer and the anode layer. The cathode buffer layer may conductively connect the cathode layer and the membrane layer. Any of the polymers in the MEA (e.g., first, second, third, and/or fourth ion conducting polymers) may comprise a composition as described herein.

In some embodiments, the cathode buffer layer has a first porosity of between about 0.01 and 95 volume percent (e.g., wherein the first porosity is formed by inert filler particles such as diamond particles, boron doped diamond particles, polyvinylidene fluoride (PVDF) particles, and Polytetrafluoroethylene (PTFE) particles).

In other embodiments, at least two of the first, second, third, and fourth ion conducting polymers are from different classes of ion conducting polymers. There are three classes of ion conducting polymers: anion conductors, cation conductors, and cation and anion conductors (cation-and-anion conductors). The ionic moiety or ionizable moiety may be selected to provide any of these classes.

The term "ion conducting polymer" is used herein to describe a polymer electrolyte having a specific conductivity greater than about 1mS/cm for anions and/or cations. The terms "anion conductor" and/or "anion conducting polymer" describe ion conducting polymers that conduct anions primarily (although there will still be a small amount of cation conduction) and have an anion migration number greater than about 0.85 at a thickness of about 100 microns. The terms "cation conductor" and/or "cation conducting polymer" describe ion conducting polymers that conduct cations primarily (e.g., there may still be occasional amounts of anion conduction) and have a cation migration number greater than about 0.85 at a thickness of about 100 microns. For ion conducting polymers described as conducting both anions and cations ("cation and anion conductors"), the number of migration of both anions and cations is no greater than about 0.85 or less than about 0.15 at a thickness of about 100 microns. The material is said to be ion conductive (anionic and/or cationic) meaning that the material is an ion conductive material.

The compositions herein may be used in a reactor. Non-limiting reactors include electrolytic cells, carbon dioxide reduction cells, electrochemical reactors, gas phase polymer-electrolyte membrane electrolytic cells, but may additionally or alternatively include any other suitable reactor. The reactor may include one or more of: an electrode (e.g., anode, cathode), a catalyst (e.g., within and/or adjacent to the cathode and/or anode), a gas diffusion layer (e.g., adjacent to the cathode and/or anode), and/or a flow field (e.g., defined within and/or adjacent to the electrode and/or gas diffusion layer, e.g., one or more channels defined opposite the cathode across the gas diffusion layer). In some embodiments, the reactor includes a membrane stack or Membrane Electrode Assembly (MEA) having one or more Polymer Electrolyte Membranes (PEM) to provide ion communication between the anode and cathode of the reactor. In certain embodiments, the reactor comprises a membrane stack comprising: a cathode layer comprising a reduction catalyst and an ion-conducting polymer; PEM membranes (e.g., bipolar membranes, unipolar membranes, etc., membranes comprising one or more anion conductors, such as an Anion Exchange Membrane (AEM), membranes comprising one or more proton and/or cation conductors, such as a proton exchange membrane, and/or membranes comprising any other suitable ion conducting polymer, membranes comprising one or more buffer layers, etc.); and an anode layer comprising an oxidation catalyst and an ion-conducting polymer. The ion conducting polymer of each layer may be the same or different ion conducting polymers. In certain embodiments, the membrane, membrane stack, membrane Electrode Assembly (MEA), polymer Electrolyte Membrane (PEM), and/or ion conducting polymer comprise the compositions described herein.

In one embodiment, a carbon dioxide reduction cell includes a Membrane Electrode Assembly (MEA). The MEA may include one or more ion conducting polymer layers (e.g., including any of the compositions described herein) and a cathode catalyst for promoting the chemical reduction of carbon dioxide to carbon monoxide.

In some constructions, the bipolar MEA has the following stacked arrangement: cathode layer/cathode buffer layer (anion conducting layer)/cation conducting layer (which may be PEM)/anode layer. In some embodiments, the bipolar MEA has a cathode layer comprising an anion conducting polymer and/or an anode layer comprising a cation conducting layer. In some embodiments, the bipolar MEA has an anode buffer layer between the cation conductive layer and the anode layer, which may contain a cation conductive material. The cathode layer, cathode buffer layer, anion conducting layer, cation conducting layer, and/or anode layer may comprise any of the compositions described herein.

In some constructions, the bipolar MEA has the following stacked arrangement: cathode layer/cation conducting layer (which may be a PEM)/anion conducting layer/anode layer. In some applications, bipolar MEA's having such an arrangement are constructed in a system for reducing an aqueous solution of carbonate and/or bicarbonate starting materials, such as carbonate and/or bicarbonate. The cathode layer, the cation conducting layer, the anion conducting layer, and/or the anode layer may comprise any of the compositions described herein.

In some constructions, the MEA has the following stacked arrangement: cathode layer/anion conducting layer/bipolar interface/cation conducting layer/anode layer. The bipolar interface may include, for example, cationic and anionic conductive polymers, a third polymer that is different from the polymers of the anionic conductive polymer layer and the cationic conductive polymer layer, a mixture of the cationic conductive polymer and the anionic conductive polymer, or cross-linking of the cationic conductive polymer and the anionic conductive polymer. The cathode layer, the anion conducting layer, the bipolar interface, the cation conducting layer, and/or the anode layer may comprise any of the compositions described herein.

In some constructions, the MEA has the following stacked arrangement: cathode layer/anion conducting layer/anode layer. In some embodiments, such MEAs have no cation conducting layer between the cathode layer and the anode layer. In some applications, an MEA containing only anion conducting material between the anode and cathode is constructed in a system for reducing carbon monoxide feedstock. The cathode layer, the anion conducting layer, and/or the anode layer can comprise any of the compositions described herein.

The compositions herein may be provided in a layer (e.g., a film layer or other herein) having any suitable porosity, including, for example, no porosity or a porosity between 0.01-95%, 0.1-95%, 0.01-75%, 1-95%, 1-90%, etc. In some embodiments, the composition may provide a layer (e.g., film) that is chemically and mechanically stable at a temperature of 80 ℃ or greater, such as 90 ℃ or greater, or 100 ℃ or greater. In other embodiments, the composition is soluble in a solvent (e.g., an organic solvent such as methanol, ethanol, isopropanol, tetrahydrofuran, chloroform, toluene, or mixtures thereof) used during layer fabrication. In particular embodiments, the compositions, their layers, or their membranes are characterized by an Ion Exchange Capacity (IEC) of about 0.2 to 3 milliequivalents/g (meq./g), such as 0.5 to 3meq./g, 1 to 3meq./g, or 1.1 to 3meq./g. In some embodiments, the compositions, their layers, or their films are characterized by a water absorption (wt%) of about 2-180 wt%, e.g., 10-180 wt%, 20-180 wt%, 50-180 wt%, 10-90 wt%, 20-90 wt%, or 50-90 wt%. In other embodiments, the compositions, their layers, or their films are characterized by an ionic conductivity greater than about 10mS/cm. In any embodiment herein, the layer, separator or film comprising the composition herein has a thickness of about 10-300 μm, such as 20-300 μm, 20-200 μm or 20-100 μm. In any of the embodiments herein, the compositions, their layers, or their films are characterized by minimal or no light absorption at wavelengths of about 350nm to 900nm, about 400nm to 800nm, or about 400nm to 900 nm.

The layer or film may be formed in any useful manner. In one embodiment, the composition (e.g., the initial polymer or ionic polymer) can be dissolved in a solvent (e.g., any of the solvents described herein, such as an organic solvent, including methanol, ethanol, isopropanol, tetrahydrofuran, chloroform, toluene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, naphthalene, a-naphthol, or a combination thereof) to form a casting solution. The casting solution may be optionally filtered, applied to a substrate, and then dried to form a film. Application to the substrate may include blade coating, solution casting, spraying, dip coating, spin coating, extrusion, melt casting, or a combination of any technique. The membrane may optionally be further treated, for example, by immersion in any of the reagents herein (e.g., ionizable reagents, crosslinking reagents, counterions, solvents (including water), and the like, and combinations thereof).

Additional uses, membranes, modules and constructions are described in U.S. application Ser. No. 15/586,182, filed 5/3/2017 by Kuhl et al, published in U.S. patent publication No. 2017-032374, entitled "Reactor with advanced architecture for the electrochemical reaction of CO ₂ CO and other chemical compounds "; U.S. application Ser. No. 63/060,583, filed 8/3 in 2020, and International application Ser. No. PCT/US2021/044378, entitled "System and method for carbon dioxide reactor control", filed 8/3 in 2020; and U.S. application Ser. No. 62/939,960 and International publication No. WO 2021/108446, entitled "Membrane electrode assembly for COx reduction," filed 11/25 in 2019, huo et al, each of which is incorporated herein by reference in its entirety.

As will be recognized by those skilled in the art from the foregoing detailed description and from the accompanying drawings and claims, modifications and changes may be made to the disclosed embodiments without departing from the scope of the disclosure as defined in the following claims.

Claims

1. A composition comprising a first structure and a second structure, wherein:

(i) The first structure comprises:

or a salt thereof, wherein:

R ⁷ and R is ⁸ Each of which is independently an electron withdrawing moiety, H, optionallyA substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted heteroaliphatic group, an optionally substituted heteroalkyl group, an optionally substituted aromatic group, an optionally substituted aryl group, or an optionally substituted arylalkylene group, wherein R ⁷ Or R is ⁸ At least one of which comprises an electron withdrawing moiety or wherein R ⁷ And R is ⁸ May together form an optionally substituted cyclic group;

ar comprises or is an optionally substituted aromatic group or an optionally substituted arylene group;

n is an integer of 1 or more;

each of ring a, ring b, and/or ring c may be optionally substituted; and

wherein ring a, ring b, ring c, R ⁷ 、R ⁸ 、R ⁹ And R is ¹⁰ Optionally comprising an ionizable or ionic moiety; and

(ii) The second structure comprises:

or a salt thereof, wherein:

R ¹ 、R ² 、R ³ 、R ⁷ 、R ⁸ 、R ⁹ and R is ¹⁰ Each of which is independently an electron withdrawing moiety, H, an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted heteroaliphatic group, an optionally substituted heteroalkyl groupOptionally substituted aromatic group, optionally substituted aryl group, optionally substituted aryloxy group or optionally substituted arylalkylene group, wherein R ⁷ And R is ⁸ Can together form an optionally substituted cyclic group or wherein R ⁹ And R is ¹⁰ May together form an optionally substituted cyclic group;

each Ak comprises or is an optionally substituted alkylene;

L、L ¹ 、L ² 、L ³ and L ⁴ Independently a linking moiety;

each of m, m1, m2, m3, and m4 is independently an integer of 1 or more;

q is 0, 1, 2 or greater;

each of rings a-i may be optionally substituted; and

wherein rings a-i, R ⁷ 、R ⁸ 、R ⁹ And R is ¹⁰ Optionally comprising an ionizable or ionic moiety.

2. The composition of claim 1, wherein the linking moiety is or comprises a covalent bond, -O-, -SO ₂ -、-NR ^N1 -, -C (O) -, optionally substituted alkylene, optionally substituted haloalkylene, optionally substituted hydroxyalkylene, optionally substituted alkyleneoxy optionally substituted heteroalkylene, optionally substituted arylene, optionally substituted aryleneoxy, or optionally substituted heterocyclodiyl.

3. The composition of claim 1, wherein the electron withdrawing moiety is optionally substituted haloalkyl, cyano, phosphate, sulfate, sulfonate, sulfonyl, difluoroborane, dihydroxyborane, thiocyanato, and piperidine

4. The composition of claim 1, wherein the first structure comprises an ionizable or ionic moiety.

5. The composition of claim 4 wherein R ⁷ Is an electron withdrawing moiety and R ⁸ Comprising an ionizable or ionic moiety.

6. The composition of claim 1, wherein the second structure comprises an ionizable or ionic moiety.

7. The composition of claim 6, wherein at least one of rings a-i comprises an ionizable or ionic moiety.

8. The composition of claim 6 wherein R ⁸ Comprising an ionizable or ionic moiety.

9. The composition of claim 1, wherein the ionizable or ionic moiety comprises-L ^A -X ^A or-L ^A -(L ^A’ -X ^A ) _L2 or-L ^A -(X ^A -L ^A’ -X ^A’ ) _L2 or-L ^A -X ^A -L ^A’ -X ^A’ or-L ^A -X ^A -L ^A’ -X ^A’ -L ^A” -X ^A” Wherein:

each L ^A 、L ^A’ And L ^A” Is a connecting structure part;

each X is ^A 、X ^A’ And X ^A” Independently comprising an acidic moiety, a basic moiety, or a polyionic moiety; and

l2 is an integer of 1 or more.

10. The composition of claim 9, wherein each L ^A 、L ^A’ And L ^A” Independently comprises optionally substituted alkylene, optionally substituted alkyleneoxy, optionally substituted heteroalkylene, optionally substituted arylene and/orOptionally substituted arylene.

11. The composition of claim 9, wherein each X ^A 、X ^A’ And X ^A” Independently comprises a sulfonic acid group, a sulfonate anion, a sulfonium cation, a carboxyl group, a carboxylate anion, a phosphonic acid group, a phosphonate anion,Cation, phosphazene->Cation, amino, ammonium cation, heterocyclic cation, piperidine->Cation, azepane->Cations or their salt forms.

12. The composition of claim 1, wherein optionally substituted arylene or optionally substituted ring a-i is substituted with one or more substituents, and wherein the substituents are selected from the group consisting of: alkyl, alkoxy, alkoxyalkyl, amino, aminoalkyl, aryl, arylalkylene, aroyl, aryloxy, arylalkoxy, cyano, hydroxy, hydroxyalkyl, nitro, halo, and haloalkyl.

13. The composition of claim 1, wherein the composition comprises a polymer or copolymer.

14. The composition of claim 1, wherein the composition comprises a film, a membrane, or a crosslinked polymer matrix.

15. An electrochemical cell comprising:

an anode;

a cathode; and

a polymer electrolyte membrane disposed between an anode and a cathode, wherein the polymer electrolyte membrane comprises the composition of claim 1.

16. A method of preparing a polymer, the method comprising:

providing a first polymer unit and optionally a second polymer unit in the presence of a friedel-crafts alkylating agent, wherein the friedel-crafts alkylating agent comprises optionally a haloalkyl group and a reactive group, thereby forming an initial polymer having reactive groups; and

substitution of the reactive groups with ionic moieties thereby providing an ionic polymer, wherein the ionic polymer comprises the composition of claim 1.

17. A method of preparing a copolymer, the method comprising:

providing a first polymer unit and a second polymer unit in the presence of a friedel-crafts alkylating agent, wherein the friedel-crafts alkylating agent comprises optionally a haloalkyl group and a reactive group, thereby forming an initial copolymer having the reactive group; and

Substitution of the reactive groups with ionic moieties thereby providing an ionic copolymer, wherein the ionic copolymer comprises the composition of claim 1.

18. A method of preparing a copolymer, the method comprising:

providing an initial copolymer having at least one aromatic group;

reacting an aryl group with a haloalkylating agent or friedel-crafts alkylating agent, wherein friedel-crafts alkylating agent comprises a reactive group, thereby forming an initial copolymer having a halo group or reactive group; and

substitution of the halo or reactive group with an ionic moiety thereby providing an ionic copolymer, wherein the ionic copolymer comprises the composition of claim 1.